Catalysts for polymerization of α-olefins, process for producing α-olefin polymers, novel transition metal compounds and catalyst components for polymerization of α-olefin

ABSTRACT

Catalysts for polymerization of α-olefin, composed of a transition metal compound, an inorganic silicate or an ion exchangeable layer compound other than silicate, and optionally an organoaluminum compound, are described. The transition metal compound is represented by formula (I):                    
     where A 1  and A 2  are each independently a conjugated 5-membered ring ligand provided that A 1  and A 2  may be the same or different in a molecule, and at least one of A 1  and A 2  forms a 7- to 10-membered condensed ring including two adjacent carbon atoms of the conjugated 5-membered ring, which condensed ring is formed by joining two adjacent substitutent groups on the conjugated 5-membered ring; Q is a bridging group of the two conjugated 5-membered rings of A 1  and A 2  at optional positions of the 5-membered rings; M is a metal atom selected from elements of Group 4-6 of the Periodic Table; and X and Z are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, and amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group.

This application is a division of application Ser. No. 08/987,768 filedDec. 9, 1997, now U.S. Pat. No. 6,340,652.

BACKGROUND OF THE INVENTION

The present invention relates to catalysts for polymerization ofα-olefin, a process for producing α-olefin polymers, novel transitionmetal compounds and catalyst components for polymerization of α-olefin.

As catalysts for polymerization of α-olefin, those comprisingmetallocene and aluminoxane have been proposed (Japanese PatentApplication Laid-open (KOKAI) No. 60-35007, Japanese Patent Publication(KOKOKU) No. 4-12283, etc.). However, since the afore-mentionedcatalysts are soluble in reaction solvent, the obtained polymer hasextremely poor properties in which the polymer has irregular particleshape, has low bulk density and includes a large amount of fine powdertherein. Therefore, in the case where these catalysts are applied togaslurry polymerization or a gas-phase polymerization of α-olefin, therehave been caused various problems concerning the production of polymers,for example, it has been difficult to conduct safe operationscontinuously, for the production of polymers.

On the other hand, in order to solve the afore-mentioned problems, therehave been proposed catalysts obtained by supporting one or both of atransition metal compound and an organoaluminum on an inorganic oxidesuch as silica or alumina or an organic substance (Japanese PatentApplications Laid-Open (KOKAI) Nos. 61-108610, 60-135408, 61-296008,3-74412 and 3-74415, etc.).

However, polymers obtained by using such catalysts have contained alarge amount of fine particles or coarse particles, and deteriorated inparticle properties such as low bulk density. Further, there arisesproblems in which the catalysts have a low catalytic activity for thepolymerization based on unit weight of solid components thereof, and theobtained polymers have disadvantages such as lower molecular weight orlower stereo regularity as compared to those obtained by using catalystsnot supported on a carrier.

SUMMARY OF THE INVENTION

The present invention has been attained for solving the afore-mentionedproblems in the prior arts.

It is an object of the present invention to provide catalysts forpolymerization of α-olefins, capable of producing α-olefin polymerswhich are free from poor in properties caused by supporting the catalyston a carrier such as low molecular weight or low stereo regularity, andwhich can show not only a narrow composition distribution but alsoexcellent transparency and mechanical strength, and to a process forproducing the α-olefin polymer by using the said catalyst.

It is another object of the present invention to provide noveltransition metal compounds and catalyst components (catalytically activecomponents) for polymerization of α-olefin.

As a result of the present inventors' earnest studies, it has been foundthat by using a catalyst comprising a specific transition metal compoundand either a specific ion exchangeable layer compound or an inorganicsilicate, the above-mentioned objects can be readily achieved.

In a first aspect of the present invention, there is provided a catalystfor polymerization of α-olefin, which comprises:

an essential component (A) of a transition metal compound,

an essential component (B) of an ion exchangeable layer compound exceptfor silicate, or an inorganic silicate, and

an optional component (C) of an organoaluminum compound, said component(A) being represented by the general formula (I):

 wherein A¹ and A² are independently a conjugate 5-membered ring ligandwith the proviso that A¹ and A² may be the same or different in amolecule, and at least one of A¹ and A² forms a 7- to 10-memberedcondensed ring including adjacent two carbon atoms of the conjugate5-membered ring, which condensed ring is formed by joining two adjacentsubstituent groups on the conjugate 5-membered ring; Q is a bridginggroup of the two conjugate 5-membered rings of A¹ and A² at optionalpositions of the 5-membered rings; M is a metal atom selected from thegroup consisting of elements belonging to Group 4-6 of the PeriodicTable; and X and Y are independently a hydrogen atom, a halogen atom, ahydrocarbon group, an amino group, a halogenated hydrocarbon group, anoxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbongroup, a phosphorus-containing hydrocarbon group or a silicon-containinghydrocarbon group.

In a second aspect of the present invention, there is provided acatalyst for polymerization of α-olefin, which comprises:

an essential component (A) of a transition metal compound,

an essential component (D) of an aluminumoxy compound, an ionic compoundcapable of reacting with the component (A) so as to convert thecomponent (A) to a cation, or a Lewis acid, and

an optional component (E) of a fine particle carrier,

said component (A) being represented by the following general formula(II), (III), (IV), (V) or (VI) included in the above general formula(I).

General Formula (II)

wherein R¹, R², R⁴ and R⁵ are independently a hydrogen atom, ahydrocarbon group having 1 to 10 carbon atoms, a silicon-containinghydrocarbon group having 1 to 18 carbon atoms or halogenated hydrocarbongroup having 1 to 18 carbon atoms; R³ and R⁶ are independently asaturated or unsaturated divalent hydrocarbon group having 3 to 10carbon atoms, which forms a condensed ring in cooperation with each of5-membered rings to which R³ and R⁶ are respectively bonded, with theproviso that at least one of R³ and R⁶ has 5 to 8 carbon atoms and formsa 7- to 10-membered condensed ring having at least one unsaturated bondderived from R³ or R⁶; R⁷ and R⁸ are independently a hydrocarbon grouphaving 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20carbon atoms, an amino group, a nitrogen-containing hydrocarbon grouphaving 1 to 20 carbon atoms or a sulfur-containing hydrocarbon grouphaving 1 to 20 carbon atoms with the proviso that at least one of R⁷ andR⁸ is the halogenated hydrocarbon group having 1 to 20 carbon atoms; mand n are independently an integer of 0 to 20 with the proviso that mand n are not 0 at the same time; Q is a bridging group of the two5-membered rings, and is a divalent hydrocarbon group having 1 to 20carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20carbon atoms, a silylene or an oligosilylene group which may have ahydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbonatoms or a germylene group which may have a hydrocarbon group orhalogenated hydrocarbon group having 1 to 20 carbon atoms; X and Y areindependently a hydrogen atom, a halogen atom, a hydrocarbon grouphaving 1 to 20 carbon atoms, a silicon-containing hydrocarbon grouphaving 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20carbon atoms, an amino group or a nitrogen-containing hydrocarbon grouphaving 1 to 20 carbon atoms; and M is a transition metal selected fromthe group consisting of elements belonging to Group 4-6 of the PeriodicTable.

General Formula (III)

wherein R¹, R², R⁴, R⁵, Q, X, and M have the same meanings as defined inthe above general formula (II); R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶are independently a hydrocarbon group having 1 to 20 carbon atoms or ahalogenated hydrocarbon group having 1 to 20 carbon atoms; and Ar is anaryl group which may be substituted, with the proviso that at least oneof the two 7-membered rings is bonded to the halogenated hydrocarbongroup having 1 to 20 carbon atoms.

General Formula (IV)

wherein R¹ and R⁴ are independently a hydrocarbon group having 7 to 12carbon atoms, a silicon-containing hydrocarbon group having 8 to 18carbon atoms or a halogenated hydrocarbon group having 7 to 12 carbonatoms; R² and R⁵ are independently a hydrogen atom, a hydrocarbon grouphaving 1 to 10 carbon atoms, a silicon-containing hydrocarbon grouphaving 1 to 18 carbon atoms or a halogenated hydrocarbon group having 1to 18 carbon atoms; R³ and R⁶ are independently a saturated orunsaturated divalent hydrocarbon group having 3 to 10 carbon atoms andforms a condensed ring in cooperation with 5-membered rings to which R³and R⁶ are respectively bonded, with the proviso that at least one of R³and R⁶ has 5 to 10 carbon atoms and forms a 7- to 10-membered condensedring having at least one unsaturated bond derived from R³ or R⁶; R⁷ andR⁸ are independently a hydrocarbon group having 1 to 20 carbon atoms, anoxygen-containing hydrocarbon group having 1 to 20 carbon atoms, anamino group, a nitrogen-containing hydrocarbon group having 1 to 20carbon atoms or a sulfur-containing hydrocarbon group having 1 to 20carbon atoms; m and n are independently an integer of 0 to 20 with theproviso that m and n are not 0 at the same time, and when m or n is aninteger of not less than 2, the R⁷ or the R⁸ may be bonded to each otherto form a ring; Q is a bridging group of the two 5-membered rings, andis a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalenthalogenated hydrocarbon group having 1 to 20 carbon atoms, a silylene oran oligosilylene group which may be substituted with a hydrocarbon grouphaving 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1to 20 carbon atoms, or a germylene group which may be substituted with ahydrocarbon group having 1 to 20 carbon atoms or a halogenatedhydrocarbon group having 1 to 20 carbon atoms; X and Y are independentlya hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20carbon atoms, a silicon-containing hydrocarbon group having 1 to 20carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbonatoms, an oxygen-containing hydrocarbon group having 1 to 20 carbonatoms, an amino group or a nitrogen-containing hydrocarbon group having1 to 20 carbon atoms; and M is a transition metal selected from thegroup consisting of elements belonging to Group 4-6 of the PeriodicTable.

General Formula (V)

wherein R¹ and R⁴ are independently a hydrocarbon group having 7 to 12carbon atoms, a silicon-containing hydrocarbon group having 8 to 18carbon atoms or a halogenated hydrocarbon group having 7 to 12 carbonatoms; R² and R⁵ are independently a hydrogen atom, a hydrocarbon grouphaving 1 to 10 carbon atoms, a silicon-containing hydrocarbon grouphaving 1 to 18 carbon atoms or a halogenated hydrocarbon group having 1to 18 carbon atoms.; R³ and R⁶ are independently a saturated orunsaturated divalent hydrocarbon group having 3 to 10 carbon atoms andforms a condensed ring in cooperation with 5-membered rings to which R³and R⁶ are respectively bonded, with the proviso that at least one of R³and R⁶ has 5 to 10 carbon atoms and forms a 7- to 10-membered condensedring having at least one unsaturated bond derived from R³ or R⁶; R⁷ andR⁸ are independently a hydrocarbon group having 1 to 20 carbon atoms, anoxygen-containing hydrocarbon group having 1 to 20 carbon atoms, anamino group, a nitrogen-containing hydrocarbon group having 1 to 20carbon atoms or a sulfur-containing hydrocarbon group having 1 to 20carbon atoms; m and n are independently an integer of 0 to 20 with theproviso that m and n are not 0 at the same time, and when m or n is aninteger of not less than 2, the R⁷ or the R⁸ may be bonded to each otherto form a ring; Q is a bridging group of the two 5-membered rings, andis a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalenthalogenated hydrocarbon group having 1 to 20 carbon atoms, a silylene oran oligosilylene group which may be substituted with a hydrocarbon grouphaving 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1to 20 carbon atoms, or a germylene group which may be substituted with ahydrocarbon group having 1 to 20 carbon atoms or a halogenatedhydrocarbon group having 1 to 20 carbon atoms; X and Y are independentlya hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20carbon atoms, a silicon-containing hydrocarbon group having 1 to 20carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbonatoms, an oxygen-containing hydrocarbon group having 1 to 20 carbonatoms, an amino group or a nitrogen-containing hydrocarbon group having1 to 20 carbon atoms; and M is a transition metal selected from thegroup consisting of elements belonging to Group 4-6 of the PeriodicTable.

General Formula (VI)

wherein R¹, R², R⁴ and R⁵ are independently a hydrogen atom, ahydrocarbon group having 1 to 10 carbon atoms, a silicon-containinghydrocarbon group having 1 to 18 carbon atoms or a halogenatedhydrocarbon group having 1 to 18 carbon atoms; R³ and R⁶ areindependently a saturated or unsaturated divalent hydrocarbon grouphaving 3 to 10 carbon atoms and forms a condensed ring in cooperationwith 5-membered rings to which R³ and R⁶ are respectively bonded, withthe proviso that at least one of R³ and R⁶ has 5 to 8 carbon atoms andforms a 7- to 10-membered condensed ring having at least one unsaturatedbond derived from R³ or R⁶; R⁷ and R⁸ are independently a hydrocarbongroup having 1 to 20 carbon atoms, an oxygen-containing hydrocarbongroup having 1 to 20 carbon atoms, an amino group, a nitrogen-containinghydrocarbon group having 1 to 20 carbon atoms or a sulfur-containinghydrocarbon group having 1 to 20 carbon atoms; Q is a silicon atom, agermanium atom or a tin atom; A is a divalent unsaturated hydrocarbongroup having 3 to 12 carbon atoms and forms a ring in cooperation withthe Q to which A is bonded; R^(a) is a saturated or unsaturatedhydrocarbon group having 1 to 10 carbon atom; m and n are independentlyan integer of 0 to 20 with the proviso that m and n are not 0 at thesame time, that when m or n is an integer of not less than 2, the R⁷ orthe R⁸ may be bonded to each other to form a ring; 1 is an integer of 0to 22, when 1 is an integer of not less than 2, the R^(a) may be bondedto each other to form a ring; X and Y are independently a hydrogen atom,a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, asilicon-containing hydrocarbon group having 1 to 20 carbon atoms, ahalogenated hydrocarbon group having 1 to 20 carbon atoms, anoxygen-containing hydrocarbon group having 1 to 20 carbon atoms, anamino group or a nitrogen-containing hydrocarbon group having 1 to 20carbon atoms; and M is a transition metal selected from the groupconsisting of elements belonging to Group 4-6 of the Periodic Table.

In a third aspect of the present invention, there is provided a processfor producing an α-olefin polymer, comprising bringing an α-olefin intocontact with any of the catalysts defined in the afore-mentioned firstand second aspects to conduct the polymerization or copolymerization ofthe α-olefin.

In a fourth aspect of the present invention, there is provided a noveltransition metal compound represented by the afore-mentioned generalformula (II).

In a fifth aspect of the present invention, there is provided a noveltransition metal compound represented by the afore-mentioned generalformula (III).

In a sixth aspect of the present invention, there is provided a noveltransition metal compound represented by the afore-mentioned generalformula (IV).

In a seventh aspect of the present invention, there is provided a noveltransition metal compound represented by the afore-mentioned generalformula (V).

In an eighth aspect of the present invention, there is provided a noveltransition metal compound represented by the afore-mentioned generalformula (VI).

In a ninth aspect of the present invention, there is provided a catalystcomponent for polymerization of α-olefin which comprises a transitionmetal compound represented by the afore-mentioned general formula (II).

In a tenth aspect of the present invention, there is provided a catalystcomponent for polymerization of α-olefin which comprises a transitionmetal compound represented by the afore-mentioned general formula (III).

In an eleventh aspect of the present invention, there is provided acatalyst component for polymerization of α-olefin which comprises atransition metal compound represented by the afore-mentioned generalformula (IV).

In a twelfth aspect of the present invention, there is provided acatalyst component for polymerization of α-olefin which comprises atransition metal compound represented by the afore-mentioned generalformula (V).

In a thirteenth aspect of the present invention, there is provided acatalyst component for polymerization of α-olefin which comprises atransition metal compound represented by the afore-mentioned generalformula (VI).

DETAILED DESCRIPTION OF THE INVENTION

The present invention is described in detail below.

The catalyst for polymerization of α-olefin according to the presentinvention comprises a specific transition metal compound (component A)as an essential component.

First, the component A of transition metal compound is explained below.In the present invention, as the transition metal compound, there can beused those compounds represented by the general formula (I):

In the afore-mentioned general formula (I), A¹ and A² are conjugate5-membered ring ligands with the proviso that A¹ and A² may be thesame-or different in a molecule and at least one of A¹ and A² forms a 7-to 10-membered condensed ring including adjacent two carbon atoms of theconjugate 5-membered ring, which condensed ring is formed by joining twoadjacent substituent groups on the conjugate 5-membered ring. Further,the conjugate 5-membered ring ligands represented by A¹ and A² may havesubstituent groups bonded to carbon atoms other than those bonded to thegroup Q.

An typical example of the above conjugate 5-membered ring ligands is acyclopentadienyl group. The cyclopentadienyl group may be anunsubstituted one, i.e., “C₅H₄—” having four hydrogen atoms, or may besubstituted ones in which one or more of the hydrogen atoms aresubstituted by any substituent groups, as described above.

Examples of the substituent groups are hydrocarbon groups having 1 to 20carbon atoms, preferably 1 to 15 carbon atoms. Specific examples of thehydrocarbon groups may include a methyl group, an ethyl group, a propylgroup, a butyl group, a hexyl group, an octyl group, a phenyl group, anaphthyl group, a butenyl group, a butadienyl group, a triphenylcarbylgroup or the like.

The afore-mentioned hydrocarbon groups may be monovalent groups bondedto the cyclopentadienyl group. Further, the two hydrocarbon substituentgroups may be bonded with each other at end positions thereof to form acondensed ring. Typical examples of the cyclopentadienyl groups havingthe condensed ring may include indene, fluorene, azulene or derivativesthereof. Incidentally, in the present invention, the transition metalcompounds used are required to have at least one 7- to 10-membered ringas the condensed ring, as described in detail hereinafter.

As the substituent groups other than the afore-mentioned hydrocarbongroups, there can be exemplified hydrocarbon groups containing silicon,oxygen, nitrogen, phosphorus, boron, sulfur or the like. Typicalexamples of the hydrocarbon residues may include a methoxy group, anethoxy group, a phenoxy group, a furyl group, a trimethylsilyl group, adiethylamino group, a diphenylamino group, a pyrazolyl group, an indolylgroup, a carbazolyl group, a dimethylphosphino group, adiphenylphosphino group, a diphenylboron group, a dimethoxyboron group,a thienyl group or the like.

As other substituent groups, there can be exemplified halogen,halogen-containing hydrocarbons or the like. Typical examples of theother substituent groups may include a chlorine atom, a bromine atom, afluorine atom, a trichloromethyl group, a thrifluoromethyl group, afluorophenyl group, a pentafluorophenyl group or the like.

Meanwhile, in the transition metal compounds used in the presentinvention, at least one of the conjugate 5-membered ring ligands A¹ andA² has a 7- to 10-membered condensed ring including adjacent two carbonatoms thereof and the condensed ring is formed by joining two adjacentsubstituent groups on the conjugate 5-membered ring. That is, at leastone of A¹ and A² must form a 7- to 10-membered condensed ring whichincludes adjacent two carbon atoms of the conjugate 5-membered ringligand.

Examples of the afore-mentioned ligands which constitute at least one ofA¹ and A², may include a hydroazulenyl group, a methylhydroazulenylgroup, an ethylhydroazulenyl group, a dimethylhydroazulenyl group, amethylethylhydroazulenyl group, a methylisopropylhydroazulenyl group, amethylphenylisopropylhydroazulenyl group, various hydrogenated azulenylgroups, a bicyclo-[6.3.0]-undecanyl group, amethyl-bicyclo-[6.3.0]-undecanyl group, anethyl-bicyclo-[6.3.0]-undecanyl group, aphenyl-bicyclo-[6.3.0]-undecanyl group, amethylphenyl-bicyclo-[6.3.0]-undecanyl group, anethylphenyl-bicyclo-[6.3.0]-undecanyl group, amethyldiphenyl-bicyclo-[6.3.0]-undecanyl group, amethyl-bicyclo-[6.3.0]-undecadienyl group, amethylphenyl-bicyclo-[6.3.0]-undecadienyl group, anethylphenyl-bicyclo-[6.3.0]-undecadienyl group, amethylisopropyl-bicyclo-[6.3.0]-undecadienyl group, abicyclo-[7.3.0]-dodecanyl group or derivatives thereof, abicyclo-[7.3.0]-dodecadienyl group or derivatives thereof, abicyclo-[8.3.0]-tridecanyl group or derivatives thereof, abicyclo-[8.3.0]-tridecadienyl group or derivatives thereof, or the like.

The afore-mentioned groups may further have substituent groups such ashydrocarbon groups, hydrocarbon groups containing silicon, oxygen,nitrogen, phosphorus, boron, sulfur or the like, halogens orhalogen-containing hydrocarbons, etc., as described hereinbefore.

The Q is a bridging group of the two conjugate 5-membered rings of A¹and A² at optional positions of the 5-membered rings. That is, the Q isa divalent bonding group and acts to cross-link the two conjugate5-membered rings with each other. The kinds of bonding groups Q are notparticularly restricted. Examples of the bonding groups Q may include(a) divalent hydrocarbon or halogenated hydrocarbon groups havingusually 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, morespecifically, unsaturated divalent hydrocarbon groups such as alkylenegroups, cycloalkylene groups, arylene groups, haloalkylene groups orhalocycloalkylene groups; (b) silylene groups or oligosilylene groups;(c) silylene groups or oligosilylene groups substituted with hydrocarbonor halogenated hydrocarbon groups having usually 1 to 20 carbon atoms,preferably 1 to 12 carbon atoms; (d) germylene groups; (e) germylenegroups substituted with hydrocarbon or halogenated hydrocarbon groupshaving usually 1 to 20 carbon atoms; or the like. Among them, alkylenegroups, cycloalkylene groups, arylene groups, silylene groupssubstituted with hydrocarbon groups or germylene groups substituted withhydrocarbon groups are preferred.

The M represents a transition metal atom selected from the groupconsisting of elements belonging to Group 4-6 of the Periodic Table.Among them, Group 4 transition metals such as titanium, zirconium orhafnium are preferred, and zirconium or hafnium is more preferred.

The X and Y represent independently a hydrogen atom, a halogen atom, ahydrocarbon group, an amino group, a halogenated hydrocarbon group, anoxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbongroup, a phosphorus-containing hydrocarbon group or a silicon-containinghydrocarbon group. Each of the afore-mentioned hydrocarbon groups mayhave usually 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms.Specific examples of the preferred X and Y may include a hydrogen atom,a chlorine atom, a methyl group, an isobutyl group, a phenyl group, adimethyl amino group, a diethyl amino group or the like.

Some groups of the transition metal compounds represented by theaforementioned general formula (I), i.e., the transition metal compoundsrepresented by the below-mentioned general formula (II), (III), (IV),(V) and (VI) are novel compounds.

The novel transition metal compounds classified into the first group isexplained below. The transition metal compounds of the first group isrepresented by the general formula (II):

The novel transition metal compound represented by the general formula(II) involves compounds (a) in which the 5-membered ring ligand havingsubstituent groups R¹, R² and R³ and the 5-membered ring ligand havingsubstituent groups R⁴, R⁵ and R⁶ are asymmetrical with respect to aplane containing M, X and Y when viewed as to the relative positionsthereof through the group Q, and compounds (b) in which the 5-memberedring ligand having substituent groups R¹, R² and R³ and the 5-memberedring ligand having substituent groups R⁴, R⁵ and R⁶ are symmetrical withrespect to a plane containing M, X and Y when viewed as to the relativepositions thereof through the group Q.

In order to produce α-olefin polymers having a high molecular weight anda high melting point, the afore-mentioned compounds (a), i.e., thecompounds in which the two 5-membered ring ligands do not have arelationship of real and mirror images with respect to the planecontaining M, X and Y, can be preferably used. Also, in case of use ofthe novel transition metal compound represented by the following generalformulae (III), (IV), (V) and (VI).

In the general formula (II), R¹, R², R⁴ and R⁵ are independently ahydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, asilicon-containing hydrocarbon group having 1 to 18 carbon atoms orhalogenated hydrocarbon group having 1 to 18 carbon atoms, as describedabove.

Specific examples of the afore-mentioned hydrocarbon group having 1 to10 carbon atoms may include alkyl groups such as methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl,n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl or methylcyclohexyl;alkenyl groups such as vinyl, propenyl or cyclohexenyl; aralkyl groupssuch as benzyl, phenylethyl or phenylpropyl; aryl-alkenyl groups such astrans-styryl; aryl groups such as phenyl, tolyl, dimethylphenyl,ethylphenyl, trimethylphenyl, 1-naphthyl or 2-naphthyl; or the like.

Specific examples of the afore-mentioned silicon-containing hydrocarbonatom having 1 to 18 carbon atoms may include trialkylsilyl groups suchas trimethylsilyl, triethylsilyl or t-butyldimethylsilyl; triarylsilylgroups such as triphenylsilyl; (alkyl)(aryl)silyl groups such asdimethylphenylsilyl; alkylsilylalkyl groups such asbis(trimethylsilyl)methyl; or the like.

As the afore-mentioned halogen atoms contained in the halogenatedhydrocarbon groups having 1 to 18 carbon atoms, there can be used afluorine atom, a chlorine atom, a bromine atom and an iodine atom. Inthe case where the halogen atom contained in the halogenated hydrocarbongroup is, for example, a fluorine atom, the fluorine atom can be bondedto optional position(s) of the hydrocarbon group. Specific examples ofthe halogenated hydrocarbon groups may include fluoromethyl,difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl,2,2,2-trifluoromethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl,pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl,1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, o-, m- orp-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, 2,4-,3,5-, 2,6- or 2,5-difluorophenyl, 2,4-, 3,5-, 2,6- or2,5-dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl,pentafluorophenyl, pentachlorophenyl, 4-fluoronaphthyl,4-chloronaphthyl, 2,4-difluoronaphthyl, heptafluoro-1-naphthyl,heptachloro-1-naphthyl, o-, m- or p-trifluoromethylphenyl, o-, m- orp-trichloromethylphenyl, 2,4-, 3,5-, 2,6- or2,5-bis(trifluoromethyl)phenyl, 2,4-, 3,5-, 2,6- or2,5-bis(trichloromethyl)phenyl, 2,4,6-tris(trifluoromethyl)phenyl,4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl,2,4-bis(trifluoromethyl)naphthyl or the like.

Among them, as the R¹ and R⁴, hydrocarbon groups having 1 to 7 carbonatoms such as methyl, ethyl, propyl, butyl or benzyl are preferred, andas the R² and R⁵, a hydrogen atom is preferred.

In the general formula (II), R³ and R⁶ are independently a saturated orunsaturated divalent hydrocarbon group having 3 to 10 carbon atoms andforms a condensed ring in cooperation with the 5-membered ring to whichthe R³ or R⁶ is bonded. The condensed ring formed by the R³ or R⁶ may bea 5- to 12-membered ring. However, it is essentially required that atleast one of the R³ and R⁶ has 5 to 8 carbon atoms and forms a 7- to10-membered condensed ring having at least one unsaturated bond derivedfrom the R³ or R⁶. In this case, it is preferred that both of thecondensed rings are 7- to 10-membered rings.

Specific examples of the R³ and R⁶ may include divalent saturatedhydrocarbon groups such as trimethylene, tetramethylene, pentamethylene,hexamethylene or heptamethylene; divalent unsaturated hydrocarbon groupssuch as propenylene, 2-butenylene, 1,3-butadienylene, 1-pentenylene,2-pentenylene, 1,3-pentadienylene, 1,4-pentadienylene, 1-hexenylene,2-hexenylene, 3-hexenylene, 1,3-hexadienylene, 1,4-hexadienylene,1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene or1,3,5-hexatrienylene; or the like. Among them, pentamethylene,1,3-pentadienylene, 1,4-pentadienylene or 1,3,5-hexatrienylene arepreferred, and 1,3-pentadienylene or 1,4-pentadienylene are especiallypreferred.

In the general formula (II), R⁷ and R⁸ are independently a hydrocarbongroup having 1 to 20 carbon atoms, a halogenated hydrocarbon grouphaving 1 to 20 carbon atoms, an oxygen-containing hydrocarbon grouphaving 1 to 20 carbon atoms, an amino group, a nitrogen-containinghydrocarbon group having 1 to 20 carbon atoms or a sulfur-containinghydrocarbon group having 1 to 20 carbon atoms. However, it is requiredthat at least one of the R⁷ and R⁸ is the halogenated hydrocarbon grouphaving 1 to 20 carbon atoms.

Specific examples of the afore-mentioned hydrocarbon group having 1 to20 carbon atoms may include alkyl groups such as methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl,n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl or methylcyclohexyl;alkenyl groups such as vinyl, propenyl or cyclohexenyl; aralkyl groupssuch as benzyl, phenylethyl or phenylpropyl; arylalkenyl groups such astrans-styryl; aryl groups such as phenyl, tolyl, dimethylphenyl,ethylphenyl, trimethylphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl,phenanthryl or anthryl; or the like. Among them, alkyl groups having 1to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl,i-butyl, s-butyl, t-butyl or cyclopropyl, and aryl groups having 6 to 20carbon atoms such as phenyl, tolyl, dimethylphenyl, ethylphenyl,trimethylphenyl, 1-naphthyl or 2-naphthyl are preferred.

As the afore-mentioned halogen atoms contained in the halogenatedhydrocarbon groups having 1 to 20 carbon atoms, there can be used afluorine atom, a chlorine atom, a bromine atom and an iodine atom. Inthe case where the halogen atom contained in the halogenated hydrocarbongroup is, for example, a fluorine atom, the fluorine atom can be bondedto optional position(s) of the hydrocarbon group. Specific examples ofthe halogenated hydrocarbon groups may include fluoromethyl,difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl,2,2,2-trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl,pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl,1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, -o-, m- orp-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, 2,4-,3,5-, 2,6- or 2,5-difluorophenyl, 2,4-, 3,5-, 2,6- or2,5-dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl,pentafluorophenyl, pentachlorophenyl, 4-fluoronaphthyl,4-chloronaphthyl, 2,4-difluoronaphthyl, heptafluoro-1-naphthyl,heptachloro-1-naphthyl, o-, m- or p-trifluoromethylphenyl, o-, m- orp-trichloromethylphenyl, 2,4-, 3,5-, 2,6- or2,5-bis(trifluoromethyl)phenyl, 2,4-, 3,5-, 2,6- or2,5-bis(trichloromethyl)phenyl, 2,4,6-tris(trifluoromethyl)phenyl,4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl,2,4-bis(trifluoromethyl)naphthyl or the like. Among them, fluorinatedhydrocarbon groups or chlorinated hydrocarbon groups are preferred, ando-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl or o-, m- orp-trifluoromethylphenyl are especially preferred.

Specific examples of the afore-mentioned oxygen-containing hydrocarbongroups having 1 to 20 carbon atoms may include alkoxy groups such asmethoxy, ethoxy, propoxy, cyclopropoxy or butoxy; aryloxy groups such asphenoxy, methylphenoxy, dimethylphenoxy or naphthoxy; arylalkoxy groupssuch as phenylmethoxy or naphthylmethoxy; oxygen-containing heterocyclicgroups such as furyl group; or the like.

Specific examples of the afore-mentioned nitrogen-containing hydrocarbongroups having 1 to 20 carbon atoms may include alkylamino groups such asmethylamino, dimethylamino, ethylamino or diethylamino; arylamino groupssuch as phenylamino or diphenylamino; (alkyl)(aryl)amino groups such as(methyl)(phenyl) amino; nitrogen-containing heterocyclic groups such aspyrazolyl or indolyl; or the like.

In the general formula (II), m and n are independently an integer of 0to 20, preferably 1 to 5. If m and/or n are an integer of 2 to 20, aplurality of the R⁷ or R⁸ may be the same or different. The integers mand n are not zero at the same time. That is, it is essential that thedivalent groups R³ and/or R⁶ have the afore-mentioned substituent groupsR⁷ or R⁸, and the substituent groups R⁷ and/or R⁸ are the halogenatedhydrocarbon groups having 1 to 20 carbon atoms. In addition, when theinteger m or n is not less than 2, the R⁷ or the R⁸ may be bonded toeach other to form an additional ring. The substituent group R⁷ or R⁸may be bonded to any position of R³ or R⁶, but it is preferred that thesubstituent groups R⁷ or R⁸ is bonded to the carbon atoms of R³ or R⁶,adjacent to the 5-membered ring (the carbon at α-position).

In the general formula (II), Q is a bridging group of the two 5-memberedrings, and is a divalent hydrocarbon group having 1 to 20 carbon atoms,a silylene or an oligosilylene group which may have a hydrocarbon orhalogenated hydrocarbon group having 1 to 20 carbon atoms or a germylenegroup which may have a hydrocarbon group or halogenated hydrocarbongroup having 1 to 20 carbon atoms. When silylene group or germylenegroup has two hydrocarbon or halogenated hydrocarbon groups, thosegroups may be bonded to each other to form a ring.

Specific examples of the group Q may include alkylene groups such asmethylene, methylmethylene, dimethylmethylene, 1,2-ethylene,1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene or1,4-cyclohexylene; arylalkylene groups such as (methyl)(phenyl)methyleneor diphenylmethylene; silylene groups; alkylsilylene groups such asmethylsilylene, dimethylsilylene, diethylsilylene, di(n-propyl)silylene,di(i-propyl)silylene or di(cyclohexyl)silylene; (alkyl)(aryl)silylenegroups such as methylphenylsilylene or methyltolylsilylene; arylsilylenegroups such as diphenylsilylene; haloalkylsilylene groups such asdi(chloromethyl)silylene or di(2-chloroethyl)silylene;(alkyl)(haloalkyl)silylene groups such asmethyl(4-chlorophenyl)silylene; di(haloalkyl)silylene groups such asdi(4-chlorophenyl)silylene or bis(3,5-dichlorophenyl)silylene; germylenegroups; alkyl germylene groups obtained by substituting germanium for asilicon atom of the afore-mentioned silylene groups having the C₁ to C₂₀hydrocarbon groups; alkyl aryl germylene groups or aryl germylenegroups; or the like. Among them, the silylene groups having the C₁ toC₂₀ hydrocarbon groups or the germylene groups having the C₁ to C₂₀hydrocarbon groups are preferred, and the alkylsilylene groups, thealkyl arylsilylene groups or the arylsilylene groups are especiallypreferred.

In the general formula (II), X and Y represent independently a hydrogenatom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,silicon-containing hydrocarbon group having 1 to 20 carbon atoms, ahalogenated hydrocarbon group having 1 to 20 carbon atoms, anoxygen-containing hydrocarbon group having 1 to 20 carbon atoms, anamino group or a nitrogen-containing hydrocarbon group having 1 to 20carbon atoms.

As the afore-mentioned halogen atoms, there can be used a fluorine atom,a chlorine atom, a bromine atom and an iodine atom. As theafore-mentioned hydrocarbon groups having 1 to 20 carbon atoms and thehalogenated hydrocarbon group having 1 to 20 carbon atoms, there can beexemplified the same hydrocarbon groups and halogenated hydrocarbongroups as defined above with respect to the R⁷ and R⁸.

Specific examples of the afore-mentioned silicon-containing hydrocarbongroups may include trialkylsilylmethyl groups such astrimethylsilylmethyl or triethylsilylmethyl; di(alkyl) (aryl)silylmethyl groups such as dimethylphenylsilylmethyl,diethylphenylsilylmethyl, dimethyltolylsilylmethyl; or the like.

Specific examples of the afore-mentioned oxygen-containing hydrocarbongroups having 1 to 20 carbon atoms may include alkoxy groups such asmethoxy, ethoxy, propoxy, cyclopropoxy or butoxy; aryloxy groups such asphenoxy, methylphenoxy, dimethylphenoxy or naphthoxy; arylalkoxy groupssuch as phenylmethoxy or naphthylmethoxy; or the like.

Specific examples of the afore-mentioned nitrogen-containing hydrocarbongroups having 1 to 20 carbon atoms may include alkylamino groups such asmethylamino, dimethylamino, ethylamino or diethylamino; arylamino groupssuch as phenylamino or diphenylamino; (alkyl) (aryl) amino groups suchas (methyl)(phenyl) amino; or the like.

In the general formula (II), the X and Y are preferably a hydrogen atom,a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or anitrogen-containing hydrocarbon group having 1 to 20 carbon atoms. Amongthem, the halogen atom, the hydrocarbon group having 1 to 20 carbonatoms or the nitrogen-containing hydrocarbon group having 1 to 20 carbonatoms are more preferred. Further, the especially preferred X and Y area chlorine atom, a methyl group, an i-butyl group, a phenyl group, adimethylamino group and a diethylamino group.

In the general formula (II), M represents a transition metal selectedfrom the group consisting of elements belonging to Group 4-6 of thePeriodic Table. Among them, Group 4 transition metals such as titanium,zirconium or hafnium are preferred. Further, zirconium or hafnium aremore preferred.

The novel transition metal compounds represented by the general formula(II) can be produced by optional methods according to the kinds ofsubstituent groups or bonding manners thereof. Typically, the transitionmetal compounds can be produced through the following reaction scheme.Incidentally, “H₂R_(a)” and “H₂R_(b)” in the reaction scheme have thefollowing chemical formulae:

 H₂R_(a)+n-C₄H₉Li→HR_(a)Li+C₄H₁₀

H₂R_(b)+n-C₄H₉Li→HR_(b)Li+C₄H₁₀

HR_(a)Li+HR_(b)Li+QCl₂→HR_(a)—Q—HR_(b)+2LiCl

HR_(a)—Q—HR_(b)+2(n-C₄H₉Li)→LiR_(a)—Q—LiR_(b)+2C₄H₁₀

LiR_(a)—Q—LiR_(b)+ZrCl₄→(R_(a)—Q—R_(b))ZrCl₂+2LiCl₂

In addition, the metal salts of the cyclopentadienyl compounds such asthe afore-mentioned HR_(a)Li and HR_(b)Li may be produced by additionreaction of alkyl groups or aryl groups, for example, as described inEuropean Patent No. 697418. More specifically, an alkyl lithium compoundor an aryl lithium compound is reacted with an azulene derivative in aninert solvent to produce a lithium salt of a dihydroazulenyl derivative.As the alkyl lithium compounds, there can be used methyl lithium,i-propyl lithium, n-butyl lithium, t-butyl lithium or the like. As thearyl lithium compounds, there can be used phenyl lithium, p-chlorophenyllithium, p-fluorophenyl lithium, p-trifluoromethylphenyl lithium,naphthyl lithium or the like. In addition, as the inert solvents, therecan be used hexane, benzene, toluene, diethyl ether, tetrahydrofuran ormixed solvents thereof.

Next, the novel transition metal compounds classified into the secondgroup are explained below. The transition metal compounds of the secondgroup are specific compounds among those belonging to the first group,which are represented by the general formula (III):

In the general formula (III), R¹, R², R⁴, R⁵, Q, X, Y and M have thesame meanings as defined in the above general formula (II), and R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ bonding to 7-membered ring areindependently a hydrocarbon group having 1 to 20 carbon atoms or ahalogenated hydrocarbon group having 1 to 20 carbon atoms. The Arrepresents an aryl group. However, it is required that at least one ofthe two 7-membered rings is substituted with the halogenated hydrocarbongroup having 1 to 20 carbon atoms. As the hydrocarbon groups having 1 to20 carbon atoms or the halogenated hydrocarbon groups having 1 to 20carbon atoms, there can be exemplified the same hydrocarbon groups andhalogenated hydrocarbon groups as defined above with respect to thegeneral formula (II). Specific examples of the aryl groups may include aphenyl group, a naphthyl group, an anthryl group, a phenanthryl group orthe like. These aryl groups may be substituted by 1 to 5 halogen atomsor halogenated hydrocarbon groups.

Next, the novel transition metal compounds classified into the thirdgroup are explained below. The transition metal compounds of the thirdgroup are represented by the general formula (IV):

In the general formula (IV), R¹ and R⁴ are independently a hydrogenatom, a hydrocarbon group having 1 to 6 carbon atoms, asilicon-containing hydrocarbon group having 1 to 7 carbon atoms or ahalogenated hydrocarbon group having 1 to 6 carbon atoms.

Examples of the afore-mentioned hydrocarbon groups having 1 to 6 carbonatoms may include alkyl groups such as methyl, ethyl, n-propyl,i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl,cyclopropyl, cyclopentyl or cyclohexyl; alkenyl groups such as vinyl,propenyl or cyclohexenyl; a phenyl group; or the like.

Examples of the afore-mentioned silicon-containing hydrocarbon groupshaving 1 to 7 carbon atoms may include trialkylsilyl groups such astrimethylsilyl, triethylsilyl or t-butyldimethylsilyl; alkylsilylalkylgroups such as bis(trimethylsilyl)methyl; or the like.

As the halogen atom in the afore-mentioned halogenated hydrocarbongroups having 1 to 6 carbon atoms, there may be used the same atoms asdescribed with respect to the general formula (II). In case where thehalogen atom contained in the halogenated hydrocarbon group is, forexample, a fluorine atom, the afore-mentioned halogenated hydrocarbongroups is that substituted with fluorine atom at optional position(s)thereof. Specific examples of the halogenated hydrocarbon groups mayinclude fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl,2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl,pentafluoropropyl, nonafluorobutyl, trifluorovinyl, o-, m- orp-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, 2,4-,3,5-, 2,6- or 2,5-difluorophenyl, 2,4-, 3,5-, 2,6- or2,5-dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl,pentafluorophenyl, pentachlorophenyl, or the like.

Among them, as the R¹ and R⁴, the hydrocarbon groups having 1 to 6carbon atoms such as methyl, ethyl, propyl or butyl are preferred.

In the general formula (IV), R² and R⁵ are independently a hydrogenatom, a hydrocarbon group having 1 to 10 carbon atoms, asilicon-containing hydrocarbon group having 1 to 18 carbon atoms or ahalogenated hydrocarbon group having 1 to 18 carbon atoms. Specificexamples of the substituents R² and R⁵ may be the same as thosedescribed in the general formula (II).

In the general formula (IV), R³ is a saturated or unsaturated divalenthydrocarbon group having 3 to 10 carbon atoms and forms a condensed ringin cooperation with a 5-membered ring to which R³ is bonded.Accordingly, the condensed ring formed by the R³ is a 5- to 12-memberedring. Specific examples of the R³ may include divalent saturatedhydrocarbon groups such as trimethylene, tetramethylene, pentamethyleneor hexamethylene; divalent unsaturated hydrocarbon groups such aspropenylene, 2-butenylene, 1,3-butadienylene, 1-pentenylene,2-pentenylene, 1,3-pentadienylene, 1,4-pentadienylene, 1-hexenylene,2-hexenylene, 3-hexenylene, 1,3-hexadienylene, 1,4-hexadienylene,1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene or1,3,5-hexatrienylene; or the like. Among them, pentamethylene,1,3-pentadienylene, 1,4-pentadienylene or 1,3,5-hexatrienylene arepreferred. Further, pentamethylene, 1,3-pentadienylene or1,4-pentadienylene are more preferred. Still further, 1,3-pentadienyleneor 1,4-pentadienylene are especially preferred.

That is, it is preferred that the R³ is a C₅ divalent saturated orunsaturated hydrocarbon group forms a condensed ring in cooperation withthe 5-membered ring to which the R³ is bonded. It is more preferred thatthe R³ is pentadienylene.

In the general formula (IV), R⁶ is a saturated or unsaturated divalenthydrocarbon group having 5 to 8 carbon atoms and forms a condensed ringin cooperation with a 5-membered ring to which R⁶ is bonded.Accordingly, the condensed ring formed by the R⁶ is a 7- to 10-memberedring. Specific examples of the R⁶ may include divalent saturatedhydrocarbon groups such as pentamethylene, hexamethylene orheptamethylene; divalent unsaturated hydrocarbon groups such as1-pentenylene, 2-pentenylene, 1,3-pentadienylene, 1,4-pentadienylene,1-hexenylene, 2-hexenylene, 3-hexenylene, 1,3-hexadienylene,1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene,2,5-hexadienylene or 1,3,5-hexatrienylene; or the like. Among them,pentamethylene, 1,3-pentadienylene, 1,4-pentadienylene or1,3,5-hexatrienylene are preferred. Further, pentamethylene,1,3-pentadienylene or 1,4-pentadienylene are more preferred. Stillfurther, 1,3-pentadienylene or 1,4-pentadienylene are especiallypreferred.

That is, it is preferred that the R⁶ is a C₅ divalent saturated orunsaturated hydrocarbon group forms a condensed ring in cooperation withthe 5-membered ring to which the R⁶ is bonded. It is more preferred thatthe R⁶ is pentadienylene.

In the general formula (IV), R⁷ and R⁸ are independently a hydrocarbongroup having 1 to 20 carbon atoms, an oxygen-containing hydrocarbongroup having 1 to 20 carbon atoms, an amino group, a nitrogen-containinghydrocarbon group having 1 to 20 carbon atoms or a sulfur-containinghydrocarbon group having 1 to 20 carbon atoms, with the proviso that atleast one R⁸ is present at a β- or remoter position on R⁶ with respectto the 5-membered ring. As the R⁷ and R⁸ of the general formula (IV),there may be used the same groups as those described in general formula(II) except for the halogenated hydrocarbon groups.

In the general formula (IV), m is an integer of 0 to 20 and n is aninteger of 1 to 16. When m or n is an integer of not less than 2, the R⁷or the R⁸ may be bonded to each other to form a ring. The m and n arepreferably an integer of 1 to 5, more preferably 2 to 5. In the casewhere the m and/or n are an integer of not less than 2, a plurality ofR⁷ (or a plurality of R⁸) may be the same or different. The position ofR³ to which the R⁷ is bonded or the position of R⁶ to which the R⁸ isbonded is not particularly restricted except for the afore-mentioneddefinitions concerning the bonding position of the R⁸, but it ispreferred that the R⁷ or the R⁸ is bonded to a carbon atom of the R³ orR⁶ adjacent to the 5-membered ring (i.e., carbon atom of α-position).

In the general formula (IV), Q is a bridging group of the two 5-memberedrings, and represents a divalent hydrocarbon group having 1 to 20 carbonatoms, a silylene or an oligosilylene group which may be substitutedwith a hydrocarbon group having 1 to 20 carbon atoms or a halogenatedhydrocarbon group having 1 to 20 carbon atoms, or a germylene groupwhich may be substituted with a hydrocarbon group having 1 to 20 carbonatoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Asthe Q of the general formula (IV), there may be used the same groups asthose described in general formula (II).

In the general formula (IV), X and Y are independently a hydrogen atom,a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, ahalogenated hydrocarbon group having 1 to 20 carbon atoms, asilicon-containing hydrocarbon group having 1 to 20 carbon atoms, anoxygen-containing hydrocarbon group having 1 to 20-carbon atoms, anamino group or a nitrogen-containing hydrocarbon group having 1 to 20carbon atoms. As the X and Y of the general formula (IV), there may beused the same groups as those described in general formula (II).

In the general formula (IV), M is a transition metal selected from thegroup consisting of elements belonging to Group 4-6 of the PeriodicTable. As the M of the general formula (IV), there may be used the sametransition metals as those described in general formula (II).

The novel transition metal compounds represented by the general formula(IV) can be produced by the same production method as used for thetransition metal compound represented by the general formula (II).

Next, the novel transition metal compounds classified into the fourthgroup are explained below. The transition metal compounds of the fourthgroup are represented by the general formula (V):

In the general formula (V), R¹ and R⁴ are independently a hydrocarbongroup having 7 to 12 carbon atoms, a silicon-containing hydrocarbongroup having 8 to 18 carbon atoms or a halogenated hydrocarbon grouphaving 7 to 12 carbon atoms. Specific examples of the aforementioned R¹and R⁴ may include alkyl groups such as n-heptyl,1,1,2,2-tetramethylpropyl, n-octyl, s-octyl, n-nonyl orcyclohexylmethyl; alkenyl groups such as 1-heptenyl, 2-heptenyl orcyclohexenylmethyl; aralkyl groups such as benzyl, 1-phenylethyl or2-phenylethyl; aryl groups such as o-, m- or p-tolyl or2,5-dimethylphenyl; or the like.

Specific examples of the afore-mentioned silicon-containing hydrocarbongroup having 8 to 18 carbon atoms may include trialkylsilyl groups suchas tripropylsilyl. tri-n-butylsilyl or tri-t-butylsilyl; (alkyl)(aryl)silyl groups such as dimethylphenylsilyl or methyldiphenylsilyl;alkylsilyl alkyl groups such as tris(trimethylsilyl)methyl; or the like.

As the halogen atom in the afore-mentioned halogenated hydrocarbongroups having 7 to 12 carbon atoms, there may be used the same atoms asdescribed with respect to the general formula (II). In case where thehalogen atom contained in the halogenated hydrocarbon group is, forexample, a fluorine atom, the afore-mentioned halogenated hydrocarbongroups is that substituted with fluorine atom at optional positionthereof. Specific examples of the halogenated hydrocarbon groups mayinclude 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl,4-fluoronaphthyl, 4-chloronaphthyl, 2,4-difluoronaphthyl,heptafluoro-1-naphthyl, heptachloro-1-naphthyl, o-, m- orp-trifluoromethylphenyl, o-, m- or p-trichloromethylphenyl, 2,4-, 3,5-,2,6- or 2,5-bis(trifluoromethyl)phenyl, 2,4-, 3,5-, 2,6- or2,5-bis(trichloromethyl)phenyl, 2,4,6-tris(trifluoromethyl)phenyl,4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl,2,4-bis(trifluoromethyl)naphthyl or the like.

Among them, as R¹ and R⁴, the hydrocarbon groups such as n-heptyl,benzyl or 1-phenylethyl are preferred. Further, the aralkyl groups suchas benzyl or 1-phenylethyl are more preferred.

In the general formula (V), R² and R⁵ are independently a hydrogen atom,a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containinghydrocarbon group having 1 to 18 carbon atoms or a halogenatedhydrocarbon group having 1 to 18 carbon atoms. As the R² and R⁵ of thegeneral formula (V), there may be used the same groups as described inthe general formula (II).

In the general formula (V), R³ and R⁵ are independently a saturated orunsaturated divalent hydrocarbon group having 3 to 10 carbon atoms andforms a condensed ring in cooperation with 5-membered rings to which R³and R⁶ are respectively bonded, with the proviso that at least one of R³and R⁶ has 5 to 10 carbon atoms and forms a 7- to 10-membered condensedring having at least one unsaturated bond derived from R³ or R⁶. As theR³ and R⁶ of the general formula (V), there may be used the same groupsas described in the general formula (II).

In the general formula (V), R⁷ and R⁸ are independently a hydrocarbongroup having 1 to 20 carbon atoms, an oxygen-containing hydrocarbongroup having 1 to 20 carbon atoms, an amino group, a nitrogen-containinghydrocarbon group having 1 to 20 carbon atoms or a sulfur-containinghydrocarbon group having 1 to 20 carbon atoms. As the R⁷ and R⁸ of thegeneral formula (V), there may be used the same groups as described inthe general formula (II) except for halogenated hydrocarbon groups.

In the general formula (V), m and n are independently an integer of 0 to20, preferably 1 to 5. In the case where the m and/or n is an integer of2 to 20, a plurality of R⁷ (or a plurality of R⁸) may be the same ordifferent. However, in this case, m and n are not zero at the same time.In addition, when the m or n is an integer of not less than 2, R⁷ or R⁸may be bonded to each other to form a ring. The substituent group R⁷ orR⁸ may be bonded to any position of R³ or R⁶, but it is preferred thatthe R⁷ or the R⁸ is bonded to a carbon atom of R³ or R⁶ adjacent to the5-membered ring (i.e., carbon atom of α-position).

In the general formula (V), Q is a bridging group of the two 5-memberedrings, and represents a divalent hydrocarbon group having 1 to 20 carbonatoms, a silylene or an oligosilylene group which may be substitutedwith a hydrocarbon group having 1 to 20 carbon atoms or a halogenatedhydrocarbon group having 1 to 20 carbon atoms, or a germylene groupwhich may be substituted with a hydrocarbon group having 1 to 20 carbonatoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Asthe Q of the general formula (V), there may be used the same groups asdescribed for that of the general formula (II).

In the general formula (V), X and Y are independently a hydrogen atom, ahalogen atom, a hydrocarbon group having 1 to 20 carbon atoms, ahalogenated hydrocarbon group having 1 to 20 carbon atoms, asilicon-containing hydrocarbon group having 1 to 20 carbon atoms, anoxygen-containing hydrocarbon group having 1 to 20 carbon atoms, anamino group or a nitrogen-containing hydrocarbon group having 1 to 20carbon atoms. As the X and Y of the general formula (V), there may beused the same groups as described for those of the general formula (II).

In the general formula (V), M is a transition metal selected from thegroup consisting of elements belonging to Group 4-6 of the PeriodicTable. As the M of the general formula (V), there may be used the sametransition metals as described for that of the general formula (II).

The novel transition metal compounds represented by the general formula(V) can be produced by the same production method as used for thetransition metal compound represented by the general formula (II).

Next, the novel transition metal compounds classified into the fifthgroup are explained below. The transition metal compounds of the fifthgroup are represented by the general formula (VI):

In the general formula (VI), R¹, R², R⁴ and R⁵ are independently ahydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, asilicon-containing hydrocarbon group having 1 to 18 carbon atoms or ahalogenated hydrocarbon group having 1 to 18 carbon atoms. As the R¹,R², R⁴ and R⁵ of the general formula (VI), there may be used the samegroups as described for those of the general formula (II).

In the general formula (VI), R³ and R⁶ are independently a saturated orunsaturated divalent hydrocarbon group having 3 to 10 carbon atoms andforms a condensed ring in cooperation with 5-membered rings to which R³and R⁶ are respectively bonded, with the proviso that at least one of R³and R⁶ has 5 to 8 carbon atoms and forms a 7- to 10-membered condensedring having at least one unsaturated bond derived from R³ or R⁶. As theR³ and R⁶ of the general formula (VI), there may be used the same groupsas described for those of the general formula (II) except forhalogenated hydrocarbon groups.

In the general formula (VI), R⁷ and R⁸ are independently a hydrocarbongroup having 1 to 20 carbon atoms, an oxygen-containing hydrocarbongroup having 1 to 20 carbon atoms, an amino group, a nitrogen-containinghydrocarbon group having 1 to 20 carbon atoms or a sulfur-containinghydrocarbon group having 1 to 20 carbon atoms. As the R⁷ and R⁸ of thegeneral formula (VI), there may be used the same groups as described forthose of the general formula (II).

In the general formula (VI), Q is a silicon atom, a germanium atom or atin atom. Among them, a silicon atom and a germanium atom are preferred.

In the general formula (VI), A is a divalent unsaturated hydrocarbongroup having 3 to 12 carbon atoms and forms a ring in cooperation withthe Q to which A is bonded. Specific examples of such unsaturatedhydrocarbon groups may include divalent unsaturated hydrocarbon groupssuch as propenylene, butenylene, butadienylene, pentenylene,pentadienylene, hexenylene, hexadienylene, hexatrienylene or the like.Among them, divalent hydrocarbon groups having 3 to 5 carbon atoms suchas propenylene, butenylene, butadienylene, pentenylene or pentadienyleneare preferred. Further, butadienylene is more preferred.

In the general formula (VI), R^(a) is a saturated or unsaturatedhydrocarbon group having 1 to 10 carbon atom. Specific examples of suchunsaturated hydrocarbon groups may include alkyl groups such as methyl,ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl,n-hexyl, cyclopropyl or cyclopentyl; alkenyl groups such as vinyl,propenyl, butenyl, butadienyl, hexenyl or hexadienyl; aralkyl groupssuch as benzyl, phenylethyl or phenylpropyl; arylalkenyl groups such astrans-styryl; aryl groups such as phenyl, tolyl, dimethylphenyl,ethylphenyl, trimethylphenyl, 1-naphthyl or 2-naphthyl; or the like.Among them, methyl, ethyl, n-propyl, i-propyl, propenyl or butenyl arepreferred.

In the general formula (VI), m and n are independently an integer of 0to 20. The m and n are preferably an integer of 1 to 5. In the casewhere the m and/or n are an integer of 2 to 20, a plurality of R⁷ (or aplurality of R⁸) may be the same or different. However, in this case, mand n are not zero at the same time. In addition, when the m or n is aninteger of not less than 2, R⁷ or R⁸ may be bonded to each other to forma ring. The position of R³ to which the R⁷ is bonded or the position ofR⁶ to which the R⁸ is bonded is not particularly restricted, but it ispreferred that the R⁷ or the R⁸ is bonded to a carbon atom of R³ or R⁶adjacent to the 5-membered ring (carbon atom of α-position). The 1 is aninteger of 0 to 22, preferably an integer of 1 to 10, more preferably aninteger of 1 to 4. When the 1 is an integer of 2 to 22, a plurality ofR^(a) may be the same or different. Further, when the 1 is an integer ofnot less than 2, the R^(a) may be bonded to each other to form a ring.

In the general formula (VI), X and Y are independently a hydrogen atom,a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, ahalogenated hydrocarbon group having 1 to 20 carbon atoms, asilicon-containing hydrocarbon group having 1 to 20 carbon atoms, anoxygen-containing hydrocarbon group having 1 to 20 carbon atoms, anamino group or a nitrogen-containing hydrocarbon group having 1 to 20carbon atoms. As the X and Y of the general formula (VI), there may beused the same groups as described for those of the general formula (II).

In the general formula (VI), M is a transition metal selected from thegroup consisting of elements belonging to Group 4-6 of the PeriodicTable. As the M of the general formula (VI), there may be used the sametransition metals as described for that of the general formula (II).

The novel transition metal compounds represented by the general formula(VI) can be produced by the same production method as used for thetransition metal compound represented by the general formula (II). Inthis case, in the reaction scheme exemplified for the transition metalcompound represented by the general formula (II), the QCl₂ isrepresented by the following general formula:

Specific examples of the transition metal compounds according to thepresent invention may include the below-mentioned compounds.Incidentally, although these compounds are indicated below merely bychemical names thereof, it is intended that each involves both compoundshaving symmetrical and asymmetrical stereo structures as mentionedabove. First, for better understanding of nomenclatures of thesetransition metal compounds, the structural formula of zirconium chloridecompound (1) is represented below. It should be noted that the zirconiumchloride compound is also named as “methylenebis{1,1′-(2-methyl-4-phenyl-1,4-dihydroazulenyl)} zirconium dichloride,if the nomenclature derived from a compound before complexing thereofwhich has a skeleton of 1,4-dihydroazulene is considered.

Chemical Formula

(1) methylene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(2) methylene bis{1,1′-(4-hydroazulenyl)} zirconium dichloride;

(3) methylene bis{1,1′-(2-methyl-4-hydroazulenyl)} zirconium dichloride;

(4) methylene bis{1,1′-(2,4-dimethyl-4-hydroazulenyl)} zirconiumdichloride;

(5) methylene bis{1,1′-2-ethyl-4-hydroazulenyl)} zirconium dichloride;

(6) methylene bis{1,1′-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconiumdichloride;

(7) methylene bis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(8) methylene bis{1,1′-(2,4,4-trimethyazulenyl)} zirconium dichloride;

(9) methylene bis{1,1′-(2-methyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(10) methylenebis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(11) methylene bis{1,1′-(4-methyl-4-hydroazulenyl)} zirconiumdichloride;

(12) methylene bis{1,1′-(4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(13) methylene bis{1,1′-(4-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(14) methylene bis{1,1′-(4-naphthyl-4-hydroazulenyl)} zirconiumdichloride;

(15) methylene bis{1,1′-(2-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(16) methylene bis{1,1′-(2-benzyl-4-hydroazulenyl)} zirconiumdichloride;

(17) methylene bis{1,1′-(2-styryl-4-hydroazulenyl)} zirconiumdichloride;

(18) methylene bis{1,1′-(2-t-butyl-4-hydroazulenyl)} zirconiumdichloride;

(19) methylene bis{1,1′-cyclopentacyclooctenyl) zirconium dichloride;

(20) methylene bis{1,1′-(4-methylcyclopentacyclooctenyl)} zirconiumdichloride;

(21) methylene bis{1,1′-(4-ethylcyclopentacyclooctenyl)} zirconiumdichloride;

(22) methylene bis{1,1′-(4-phenylcyclopentacyclooctenyl)} zirconiumdichloride;

(23) methylene bis{1,1′-(2-ethyl-4-phenylcyclopentacyclooctenyl)}zirconium dichloride;

(24) methylenebis{1,1′-(4-methyl-4,5,6,7,8,9-hexahydrocyclopentacyclooctenyl)}zirconium dichloride;

(25) methylene bis(9-bicyclo[8.3.0]trideca-2-methylpentaenyl) zirconiumdichloride;

(26) methylene bis(9-bicyclo[8.3.0]trideca-2,12-dimethylpentaenyl)zirconium dichloride;

(27) methylene bis (9-bicyclo[83.0]trideca-2,12-dimethyloctahydropentaenyl) zirconium dichloride;

(28) methylene bis(9-bicyclo[8.3.0]trideca-2-phenyl,12-ethylpentaenyl)zirconium dichloride;

(29) ethylene bis{1,1′-(4-hydroazulenyl)} zirconium dichloride;

(30) ethylene bis{1,1′-(2-methyl-4-hydroazulenyl)} zirconium dichloride;

(31) ethylene bis{1,1′-(2,4-dimethyl-4-hydroazulenyl)} zirconiumdichloride;

(32) ethylene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(33) ethylene bis{1,1′-(2-ethyl-4-hydroazulenyl)} zirconium dichloride;

(34) ethylene bis{1,1′-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconiumdichloride;

(35) ethylene bis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(36) ethylene bis{1,1′-(2,4,4-trimethylazulenyl} zirconium dichloride;

(37) ethylene bis{1,1′-(2-methyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(38) ethylene bis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(39) ethylene bis{1,1′-(4-methyl-4-hydroazulenyl)} zirconium dichloride;

(40) ethylene bis{1,1′-(4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(41) ethylene bis{1,1′-(4-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(42) ethylene bis{1,1′-(4-naphthyl-4-hydroazulenyl)} zirconiumdichloride;

(43) ethylene bis{1,1′-(2-phenyl-4-hydroazulenyl)} zirconium dichloride;

(44) ethylene bis{1,1′-(2-benzyl-4-hydroazulenyl)} zirconium dichloride;

(45) ethylene bis{1,1′-(2-styryl-4-hydroazulenyl)} zirconium dichloride;

(46) ethylene bis{1,1′-(2-t-butyl-4-hydroazulenyl)} zirconiumdichloride;

(47) ethylene bis(1,1′-cyclopentacyclooctenyl) zirconium dichloride;

(48) ethylene bis{1,1′-(4-methylcyclopentacyclooctenyl)} zirconiumdichloride;

(49) ethylene bis{1,1′-(4-ethylcyclopentacyclooctenyl)} zirconiumdichloride;

(50) ethylene bis{1,1′-(4-phenylcyclopentacyclooctenyl)} zirconiumdichloride;

(51) ethylene bis{1,1′-(2-ethyl-4-phenylcyclopentacyclooctenyl)}zirconium dichloride;

(52) ethylenebis{1,1′-(4-methyl-4,5,6,7,8,9-hexahydrocyclopentacyclooctenyl)}zirconium dichloride;

(53) ethylene bis(9-bicyclo[8.3.0]trideca-2-methylpentaenyl) zirconiumdichloride;

(54) ethylene bis(9-bicyclo[8.3.0]trideca-2,12-dimethylpentaenyl)zirconium dichloride,

(55) ethylenebis(9-bicyclo[8.3.0]trideca-2,12-dimethyloctahydropentaenyl) zirconiumdichloride;

(56) ethylene bis(9-bicyclo[8.3.0]trideca-2-phenyl,12-ethylpentaenyl)zirconium dichloride;

(57) ethylene (1-indenyl){1-(4-hydroazulenyl)} zirconium dichloride;

(58) ethylene {1-(2-methylindenyl)}{1-(2-methyl-4-hydroazulenyl)}zirconium dichloride;

(59) ethylene{1-(2-methyl-4,5-benzoindenyl)}1-(2,4-dimethyl-4-hydroazulenyl)}zirconium dichloride;

(60) ethylene{1-(2-methyl-4-phenylindenyl)}{1-(2-methyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(61) ethylene {1-(2-ethyl-4-phenylindenyl)}{1-(2-ethyl-4-hydroazulenyl)}zirconium dichloride;

(62) ethylene{1-(2,4-dimethylcyclopentadienyl)}{1-(2-ethyl-4-methyl-4-hydroazulenyl)}zirconium dichloride;

(63) ethylene{1-(2-methyl-4,5-benzoindenyl)}{1-(2-ethyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(64) ethylene{1-(2-methyl-4-phenylindenyl)}{1-(2,4,4-trimethylazulenyl)} zirconiumdichloride;

(65) ethylene{1-(2-methyltetrahydroindenyl)}{1-(2-methyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(66) ethylene{1-(4-t-butyl-2-methylcyclopentadienyl)}{1-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(67) ethylene{1-(2-ethyl-4-phenylindenyl)}{1-(4-methyl-4-hydroazulenyl)} zirconiumdichloride;

(68) ethylene {1-(2-phenylindenyl)}{1-(4-phenyl-4-hydroazulenyl)}zircorium dichloride;

(69) ethylene{1-(2-propyl-4-phenylindenyl)}{1-(4-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(70) ethylene {1-(2-t-butylindenyl)}{1-(4-naphthyl-4-hydroazulenyl)}zirconium dichloride;

(71) dimethylmethylene bis{1,1′-(4-hydroazulenyl)} zirconium dichloride;

(72) dimethylmethylene bis{1,1′-(2-methyl-4-hydroazulenyl)} zirconiumdichloride;

(73) dimethylmethylene bis{1,1′-(2,4-dimethyl-4-hydroazulenyl)}zirconium dichloride;

(74) dimethylmethylene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(75) dimethylmethylene bis{1,1′-(2-ethyl-4-hydroazulenyl)} zirconiumdichloride;

(76) dimethylmethylene bis{1,1′-(2-ethyl-4-methyl-4-hydroazulenyl)}zirconium dichloride;

(77) dimethylmethylene bis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(78) dimethylmethylene bis{1,1′-(2,4,4-trimethylazulenyl)} zirconiumdichloride;

(79) dimethylmethylene bis{1,1′-(2-methyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(80) dimethylmethylenebis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(81) dimethylmethylene bis{1,1′-(4-methyl-4-hydroazulenyl)} zirconiumdichloride;

(82) dimethylmethylene bis{1,1′-(4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(83) dimethylmethylene bis{1,1′-(4-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(84) dimethylmethylene bis{1,1′-(4-naphthyl-4-hydroazulenyl)} zirconiumdichloride;

(85) dimethylmethylene bis{1,1′-(2-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(86) dimethylmethylene bis{1,1′-(2-benzyl-4-hydroazulenyl)} zirconiumdichloride;

(87) dimethylmethylene bis{1,1′-(2-styryl-4-hydroazulenyl)} zirconiumdichloride;

(88) dimethylmethylene bis{1,1′-(2-t-butyl-4-hydroazulenyl)} zirconiumdichloride;

(89) dimethylmethylene bis(1,1′-cyclopentacyclooctenyl) zirconiumdichloride;

(90) dimethylmethylene bis{1,1′-(4-methylcyclopentacyclooctenyl)}zirconium dichloride;

(91) dimethylmethylene bis{1,1′-(4-ethylcyclopentacyclooctenyl)}zirconium dichloride;

(92) dimethylmethylene bis{1,1′-(4-phenylcyclopentacyclooctenyl)}zirconium dichloride;

(93) dimethylmethylenebis{1,1′-(2-ethyl-4-phenylcyclopentacyclooctenyl)} zirconium dichloride;

(94) dimethylmethylenebis{1,1′-(4-methyl-4,5,6,7,8,9-hexahydrocyclopentacyclooctenyl)}zirconium dichloride;

(95) dimethylmethylene bis(9-bicyclo[8.3.0]trideca-2-methyl pentaenyl)zirconium dichloride;

(96) dimethylmethylenebis(9-bicyclo[8.3.0]trideca-2,12-dimethylpentaenyl) zirconiumdichloride;

(97) dimethylmethylenebis(9-bicyclo[8.3.0]trideca-2,12-dimethyloctahydropentaenyl) zirconiumdichloride;

(98) dimethylmethylene bis(9-bicyclo[8.3.0]trideca-2-phenyl,12-ethylpentaenyl) zirconium dichloride;

(99) dimethylmethylene (1-indenyl)}{1-(4-hydroazulenyl)} zirconiumdichloride;

(100) dimethylmethylene{1-(2-methylindenyl)}{1-(2-methyl-4-hydroazulenyl)} zirconiumdichloride;

(101) dimethylmethylene{1-(2-methyl-4,5-benzoindenyl)}{1-(2,4-dimethyl-4-hydroazulenyl)}zirconium dichloride;

(102) dimethylmethylene{1-(2-methyl-4-phenylindenyl)}{1-(2-methyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(103) dimethylmethylene{1-(2-ethyl-4-phenylindenyl)}{1-(2-ethyl-4-hydroazulenyl)} zirconiumdichloride;

(104) dimethylmethylene{1-(2,4-dimethylcyclopentadienyl)}{1-2-ethyl-4-methyl-4-hydroazulenyl)}zirconium dichloride;

(105) dimethylmethylene{1-(2-methyl-4,5-benzoindenyl)}{1-(2-ethyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(106) dimethylmethylene{1-(2-methyl-4-phenylindenyl)}{1-(2,4,4-trimethylazulenyl)} zirconiumdichloride;

(107) dimethylmethylene{1-(2-methyltetrahydroindenyl)}{1-(2-methyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(108) dimethylmethylene{1-(4-t-butyl-2-methylcyclopentadienyl)}{1-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(109) dimethylmethylene{1-(2-ethyl-4-phenylindenyl)}{1-(4-methyl-4-hydroazulenyl)} zirconiumdichloride;

(110) dimethylmethylene{1-(2-phenylindenyl)}{1-(4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(111) dimethylmethylene{1-(2-propyl-4-phenylindenyl)}{1-(4-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(112) dimethylmethylene{1-(2-t-butylindenyl)}{1-(4-naphthyl-4-hydroazulenyl)} zirconiumdichloride;

(113) 2,3-butylene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(114) dimethylsilylene bis{1,1′-(4-hydroazulenyl)} zirconium dichloride;

(115) dimethylsilylene bis{1,1′-(2-methyl-4-hydroazulenyl)} zirconiumdichloride;

(116) dimethylsilylene bis{1,1′-(2,4-dimethyl-4-hydroazulenyl)}zirconium dichloride;

(117) dimethylsilylene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(118) dimethylsilylene bis{1,1′-(2-ethyl-4-hydroazulenyl)} zirconiumdichloride;

(119) dimethylsilylene bis{1,1′-(2-ethyl-4-methyl-4-hydroazulenyl)}zirconium dichloride;

(120) dimethylsilylene bis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(121) dimethylsilylene bis{1,1′-(2,4,4-trimethylazulenyl)} zirconiumdichloride;

(122) dimethylsilylene bis{1,1′-(2-methyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(123) dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(124) dimethylsilylene bis{1,1′-(4-methyl-4-hydroazulenyl)} zirconiumdichloride;

(125) dimethylsilylene bis{1,1′-(4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(126) dimethylsilylene bis{1,1′-(4-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(127) dimethylsilylene bis{1,1′-(4-naphthyl-4-hydroazulenyl)} zirconiumdichloride;

(128) dimethylsilylene bis{1,1′-(2-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(129) dimethylsilylene bis{1,1′-(2-benzyl-4-hydroazulenyl)} zirconiumdichloride;

(130) dimethylsilylene bis{1,1′-(2-styryl-4-hydroazulenyl)} zirconiumdichloride;

(131) dimethylsilylene bis{1,1′-(2-t-butyl-4-hydroazulenyl)} zirconiumdichloride;

(132) dimethylsilylene bis(1,1′-cyclopentacyclooctenyl) zirconiumdichloride;

(133) dimethylsilylene bis{1,1′-(4-methylcyclopentacyclooctenyl)}zirconium dichloride;

(134) dimethylsilylene bis{1,1′-(4-ethylcyclopentacyclooctenyl)}zirconium dichloride;

(135) dimethylsilylene bis{1,1′-(4-phenylcyclopentacyclooctenyl)}zirconium dichloride;

(136) dimethylsilylenebis{1,1′-(2-ethyl-4-phenylcyclopentacyclooctenyl)} zirconium dichloride;

(137) dimethylsilylenebis{1,1′-(4-methyl-4,5,6,7,8,9-hexahydrocyclopentacyclooctenyl)}zirconium dichloride;

(138) dimethylsilylene bis(9-bicyclo[8.3.0]trideca-2-methylpentaenyl)zirconium dichloride;

(139) dimethylsilylenebis(9-bicyclo[8.3.0]trideca-2,12-dimethylpentaenyl) zirconiumdichloride;

(140) dimethylsilylenebis(9-bicyclo[8.3.0]trideca-2,12-dimethyloctahydropentaenyl) zirconiumdichloride;

(141) dimethylsilylene bis(9-bicyclo[8.3.0]trideca-2-phenyl,12-ethylpentaenyl) zirconium dichloride;

(142) dimethylsilylene (1-indenyl){1-(4-hydroazulenyl)} zirconiumdichloride;

(143) dimethylsilylene{1-(2-methylindenyl)}{1-(2-methyl-4-hydroazulenyl)} zirconiumdichloride;

(144) dimethylsilylene{1-(2-methyl-4,5-benzoindenyl)}{1-(2,4-dimethyl-4-hydroazulenyl)}zirconium dichloride;

(145) dimethylsilylene{1-(2-methyl-4-phenylindenyl)}{1-(2-methyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(146) dimethylsilylene{1-(2-ethyl-4-phenylindenyl)}{1-(2-ethyl-4-hydroazulenyl)} zirconiumdichloride;

(147) dimethylsilylene{1-(2,4-dimethylcyclopentadienyl)}{1-(2-ethyl-4-methyl-4-hydroazulenyl)}zirconium dichloride;

(148) dimethylsilylene{1-(2-methyl-4,5-benzoindenyl)}{1-(2-ethyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(149) dimethylsilylene{1-(2-methyl-4-phenylindenyl)}{1-(2,4,4-trimethylazulenyl)} zirconiumdichloride;

(150) dimethylsilylene{1-(2-methyltetrahydroindenyl)}{1-(2-methyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(151) dimethylsilylene{1-(4-t-butyl-2-methylcyclopentadienyl)}{1-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(152) dimethylsilylene{1-(2-ethyl-4-phenylindenyl)}{1-(4-methyl-4-hydroazulenyl)} zirconiumdichloride;

(153) dimethylsilylene{1-(2-phenylindenyl)}{1-(4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(154) dimethylsilylene{1-(2-propyl-4-phenylindenyl)}{1-(4-isopropyl-4-hydroazulenyl)}zirconium dichloride; (155) dimethylsilylene{1-(2-t-butylindenyl)}{1-(4-naphthyl-4-hydroazulenyl)} zirconiumdichloride;

(156) (methyl)(phenyl)silylene bis{1,1′-(4-hydroazulenyl)} zirconiumdichloride;

(157) (methyl)(phenyl)silylene bis{1,1′-(2-methyl-4-hydroazulenyl)}zirconium dichloride;

(158) (methyl)(phenyl)silylene bis{1,1′-(2,4-dimethyl-4-hydroazulenyl)}zirconium dichloride;

(159) (methyl)(phenyl)silylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(160) (methyl)(phenyl)silylene bis{1,1′-(2-ethyl-4-hydroazulenyl)}zirconium dichloride;

(161) (methyl)(phenyl)silylenebis{1,1′-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconium dichloride;

(162) (methyl)(phenyl)silylenebis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(163) (methyl)(phenyl)silylene bis{1,1′-(2,4,4-trimethylazulenyl)}zirconium dichloride;

(164) (methyl)(phenyl)silylenebis{1,1′-(2-methyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;

(165) (methyl)(phenyl)silylenebis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(166) diphenylsilylene bis{1,1′-(4-hydroazulenyl)} zirconium dichloride;

(167) diphenylsilylene bis{1,1′-(2-methyl-4-hydroazulenyl)} zirconiumdichloride;

(168) diphenylsilylene bis{1,1′-(2,4-dimethyl-4-hydroazulenyl)}zirconium dichloride;

(169) diphenylsilylene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(170) diphenylsilylene bis{1,1′-(2-ethyl-4-hydroazulenyl)} zirconiumdichloride;

(171) diphenylsilylene bis{1,1′-(2-ethyl-4-methyl-4-hydroazulenyl)}zirconium dichloride;

(172) diphenylsilylene bis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(173) diphenylsilylene bis{1,1′-(2,4,4-trimethylzulenyl)} zirconiumdichloride;

(174) diphenylsilylene bis{1,1′-(2-methyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(175) diphenylsilylenebis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(176) tetramethyldisilylene bis{1,1′-(4-hydroazulenyl)} zirconiumdichloride;

(177) tetramethyldisilylene bis{1,1′-(2-methyl-4-hydroazulenyl)}zirconium dichloride;

(178) tetramethyldisilylene bis{1,1′-(2,4-dimethyl-4-hydroazulenyl)}zirconium dichloride;

(179) tetramethyldisilylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(180) tetramethyldisilylene bis{1,1′-(2-ethyl-4-hydroazulenyl)}zirconium dichloride;

(181) tetramethyldisilylene bis{1,1′-(2-ethyl-4-methyl-4-hydroazulenyl)}zirconium dichloride;

(182) tetramethyldisilylene bis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(183) tetramethyldisilylene bis{1,1′-(2,4,4-trimethylazulenyl)}zirconium dichloride;

(184) tetramethyldisilylenebis{1,1′-(2-methyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;

(185) tetramethyldisilylenebis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(186) dimethylgermylene bis{1,1′-(4-hydroazulenyl)} zirconiumdichloride;

(187) dimethylgermylene bis{1,1′-(2-methyl-4-hydroazulenyl)} zirconiumdichloride;

(188) dimethylgermylene bis{1,1′-(2,4-dimethyl-4-hydroazulenyl)}zirconium dichloride;

(189) dimethylgermylene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(190) dimethylgermylene bis{1,1′-(2-ethyl-4-hydroazulenyl)} zirconiumdichloride;

(191) dimethylgermylene bis{1,1′-(2-ethyl-4-methyl-4-hydroazulenyl)}zirconium dichloride;

(192) dimethylgermylene bis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(193) dimethylgermylene bis{1,1′-(2,4,4-trimethylazulenyl)} zirconiumdichloride;

(194) dimethylgermylenebis{1,1′-(2-methyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;

(195) dimethylgermylenebis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(196) dimethylsilylenebis{1,1′-(2-trifluoromethyl-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(197) dimethylsilylene bis{1,1′-(2-ethyl-4-indolyl-4-hydroazulenyl)}zirconium dichloride;

(198) dimethylsilylene bis{1,1′-(2-ethyl-4-phenoxy-4-hydroazulenyl)}zirconium dichloride;

(199) dimethylsilylene bis{1,1′-(2-fluoro-4-pyrazolyl-4-hydroazulenyl)}zirconium dichloride;

(200) silacyclohexylidene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(201) cyclohexylidene bis{1,1′-(2-methyl-4-furyl-4-hydroazulenyl)}zirconium dichloride.

(202) dimethylsilylenebis{1,1′-(2-benzyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(203) dimethylsilylenebis[1,1′-{2-benzyl-4-(4-chlorophenyl)-4,5,6,7,8-pentahydroazulenyl}]zirconium dichloride;

(204) dimethylsilylenebis[1,1′-{2-benzyl-4-(4-fluorophenyl)-4,5,6,7,8-pentahydroazulenyl}]zirconium dichloride; (205) dimethylsilylenebis[1,1′-{2-benzyl-4-(1-naphthyl)-4,5,6,7,8-pentahydroazulenyl}]zirconium dichloride;

(206) dimethylsilylenebis[1,1′-{2-benzyl-4-(2-naphthyl)-4,5,6,7,8-pentahydroazulenyl}]zirconium dichloride;

(207) dimethylsilylenebis{1,1′-(2-benzyl-4-phenyl-7-isopropyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(208) dimethylsilylenebis[1,1′-{2-(1-phenylethyl)-4-phenyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(209) dimethylsilylenebis[1,1′-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(210) 9-silafluorene-9,9-diylbis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(211) 1-silaindene-1,1-diylbis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(212) tetramethyl-1-silacyclopentadiene-1,1-diylbis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(213) 1-silacyclo-3-pentene-1,1-diylbis{1,1′-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(214) dimethylmethylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(215) dimethylmethylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(216) dimethylmethylene bis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;

(217) ethylene bis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}]zirconium dichloride;

(218) ethylene bis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]zirconium dichloride;

(219) ethylene bis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;

(220) trimethylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(221) trimethylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(222) trimethylene bis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;

(223) dimethylsilylenebis{1,1′-(2-methyl-4-trifluoromethyl-4-hydroazulenyl}] zirconiumdichloride;

(224) dimethylsilylenebis[1,1′-{2-methyl-4-(2-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(225) dimethylsilylenebis[1,1′-{2-methyl-4-(3-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(226) dimethylsilylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(227) dimethylsilylenebis[1,1′-{2-ethyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(228) dimethylsilylenebis[1,1′-{2-methyl-4-(2-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(229) dimethylsilylenebis[1,1′-{2-methyl-4-(3-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(230) dimethylsilylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(231) dimethylsilylenebis[1,1′-{2-ethyl-4-(4-chlorophenyl)-4-hydroazulenyl{] zirconiumdichloride;

(232) dimethylsilylenebis[1,1′-{2-methyl-4-(2-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(233) dimethylsilylenebis[1,1′-{2-methyl-4-(3-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(234) dimethylsilylenebis[1,1′-(2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(235) dimethylsilylenebis[1,1′-{2-ethyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(236) dimethylsilylenebis[1,1′-{2-methyl-4-(2,4-difluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(237) dimethylsilylenebis[1,1′-{2-methyl-4-(2,5-difluorophenyl)-4-hydroazulenyl{] zirconiumdichloride;

(238) dimethylsilylenebis[1,1′-{2-methyl-4-(2,6-difluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(239) dimethylsilylenebis[1,1′-{2-methyl-4-(3,5-difluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(240) dimethylsilylenebis[1,1′-(2-methyl-4-(2,4,6-trifluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(241) dimethylsilylene [1-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl{][1-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;

(242) dimethylsilylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-6-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(243) dimethylsilylenebis[1,1′-(2,8-dimethyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(244) dimethylsilylenebis[1,1′-(2-methyl-4-(4-chlorophenyl)-6-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(245) dimethylsilylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(246) dimethylsilylenebis[1,1′-{2,8-dimethyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(247) dimethylsilylene bis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-6-isopropyl-4-hydroazulenyl}] zirconium dichloride;

(248) dimethylsilylene bis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;

(249) dimethylsilylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(250) dimethylsilylenebis[1,1′-{2-ethyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(251) dimethylsilylenebis[1,1′-{2-ethyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(252) dimethylsilylene bis[1,1′-{2-ethyl-4-(4-trifluoromethylphenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;

(253) dimethylsilylenebis[1,1′-{2-ethyl-4-(4-chlorophenyl)-7-phenyl-4-hydroazulenyl}]zirconium dichloride;

(254) dimethylsilylenebis[1,1′-{2-ethyl-4-(4-fluorophenyl)-7-phenyl-4-hydroazulenyl}]zirconium dichloride;

(255) dimethylsilylene bis[1,1′-{2-ethyl-4-(4-trifluoromethylphenyl)-7-phenyl-4-hydroazulenyl}] zirconium dichloride;

(256) diphenylsilylenebis[1,1′-(2-ethyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(257) diphenylsilylenebis[1,1′-{2-ethyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(258) diphenylsilylene bis[1,1′-{2-ethyl-4-(4-trifluoromethylphenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;

(259) (methyl)(phenyl)silylenebis[1,1′-{2-ethyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(260) (methyl) (phenyl)silylenebis[1,1′-{2-ethyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(261) (methyl)(phenyl)silylenebis[1,1′-{2-ethyl-4-(4-trifluoromethylphenyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(262) dimethylsilylenebis[1,1′-{2-ethyl-4-(4-chlorophenyl)-7-isopropyl-4,5,6,7,8-pentahydroazulenyl}]zirconium dichloride;

(263) dimethylsilylenebis[1,1′-{2-ethyl-4-(4-fluorophenyl)-7-isopropyl-4,5,6,7,8-pentahydroazulenyl}]zirconium dichloride;

(264) dimethylsilylene bis[1,1′-(2-ethyl-4-(4-trifluoromethylphenyl)-7-isopropyl-4,5,6,7,8-pentahydroazulenyl}] zirconium dichloride;

(265) dimethylsilylene[1-{2-ethyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(266) dimethylsilylene[1-{2-ethyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(267) dimethylsilylene [1-{2-ethyl-4-(4-trifluoromethylphenyl)-7-isopropyl-4-hydroazulenyl}] {1-(2-methyl-4,5-benzoindenyl)}zirconium dichloride;

(268) dimethylsilylene[1-{2-ethyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(269) dimethylsilylene[1-{2-ethyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(270) dimethylsilylene[1-{2-ethyl-4-(4-trifluoromethylphenyl)-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(261) dimethylsilylenebis[1,1′-{2-benzyl-4-(4-chlorophenyl)-4-hydroazulenyl)}] zirconiumdichloride;

(272) dimethylsilylenebis[1,1′-{2-benzyl-4-(4-fluorophenyl)-4-hydroazulenyl)} zirconiumdichloride;

(273) dimethylsilylenebis[1,1′-{2-benzyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(274) dimethylsilylenebis[1,1′-{2-benzyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(275) diphenylsilylenebis[1,1′-{2-benzyl-4-(4-chlorophenyl)-4-hydroazulenyl)} zirconiumdichloride;

(276) diphenylsilylenebis[1,1′-{2-benzyl-4-(4-fluorophenyl)-4-hydroazulenyl)} zirconiumdichloride;

(277) (methyl) (phenyl)silylenebis[1,1′-{2-benzyl-4-(4-chlorophenyl)-4-hydroazulenyl)} zirconiumdichloride;

(278) (methyl) (phenyl)silylenebis[1,1′-{2-benzyl-4-(4-fluorophenyl)-4-hydroazulenyl)} zirconiumdichloride;

(279) dimethylsilylene [1-{2-benzyl-4-(4-chlorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(280) dimethylsilylene [1-{2-benzyl-4-(4-fluorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(281) dimethylsilylene [1-{2-benzyl-4-(4-chlorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(282) dimethylsilylene [1-{2-benzyl-4-(4-fluorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(283) dimethylsilylene bis[1,1′-{2,8-dimethyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl} zirconium dichloride;

(284) dimethylsilylenebis[1,1′-{2-methyl-4-(4-fluoro-1-naphthyl)-4-hydroazulenyl}] zirconiumdichloride;

(285) dimethylsilylenebis[1,1′-{2-methyl-4-(4-fluoro-2-naphthyl)-4-hydroazulenyl}] zirconiumdichloride;

(286) (methyl)(phenyl)silylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(287) (methyl)(phenyl)silylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(288) (methyl)(phenyl)silylenebis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(289) diphenylsilylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(290) diphenylsilylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(291) diphenylsilylenebis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(292) dimethylgermylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(293) dimethylgermylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(294) dimethylgermylenebis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(295) dimethylsilylene [1-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(296) dimethylsilylene[1-{2-ethyl-4-(4-fluorophenyl)-4-dihydroazulenyl}]{1-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(297) dimethylsilylene [1-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(298) dimethylsilylene[1-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(299) dimethylsilylene [1-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(300) dimethylsilylene [1-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4-(4-fluorophenyl)-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(301) dimethylsilylene [1-{2-ethyl-4-(4-fluorophenyl)-4-hydroazulenyl}]{1-(2-ethyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(302) dimethylsilylene [1-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(303) dimethylsilylene[1-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl}] zirconiumdichloride;

(304) dimethylsilylene [1-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(305) dimethylsilylene [1-{2-ethyl-4-(4-fluorophenyl)-4-hydroazulenyl}]{1-(2-ethyl-4-phenylindenyl)} zirconium dichloride;

(306) dimethylsilylene [1-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(307) dimethylsilylene[1-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(308) dimethylsilylene[1-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(309) dimethylsilylene [1-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(310) dimethylsilylene [1-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(311) dimethylsilylene[1-{2-methyl-4-(4-chlorophenyl)-4,5,6,7,8-pentahydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(312) dimethylsilylene [1-{2-methyl-4-(4-fluorophenyl) indenyl}]{1-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(313) dimethylsilylene [1-{2-ethyl-4-(4-fluorophenyl) indenyl}]{1-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(314) dimethylsilylene [1-{2-methyl-4-(4-chlorophenyl) indenyl}]{1-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(315) dimethylsilylene [1-{2-methyl-4-(4-trifluoromethylphenyl)indenyl}] {1-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(316) dimethylsilylene [1-{2-methyl-4-(4-trifluoromethylphenyl)indenyl}][1-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl] zirconium dichloride;

(317) dimethylsilylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)cyclopentacyclooctenyl} zirconiumdichloride;

(318) dimethylsilylenebis[1,1′-{2-ethyl-4-(4-chlorophenyl)cyclopentacyclooctenyl} zirconiumdichloride;

(319) dimethylsilylenebis[1,1′-{2-methyl-5-(4-trifluoromethylphenyl)cyclopentacyclooctenyl}zirconium dichloride.

(320) 9-silafluorene-9,9-diylbis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(321) 9-silafluorene-9,9-diylbis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(322) 1-silaindene-1,1-diylbis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(323) 1-silaindene-1,1-diylbis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(324) tetramethyl-1-silacyclopentadiene-1,1-diylbis[1,1′-(2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(325) tetramethyl-1-silacyclopentadiene-1,1-diylbis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(326) 1-silacyclo-3-pentene-1,1-diylbis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(327) 1-silacyclo-3-pentene-1,1-diylbis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(328) (4-fluorophenyl)methylsilylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl] zirconiumdichloride;

(329) (4-chlorophenyl)methylsilylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride;

(330) (chloromethyl)methylsilylenebis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride;

(331) (4-fluorophenyl)methylsilylene[1-(2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}]{1-(2-ethyl-4-phenylindenyl)} zirconium dichloride;

(332) dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(333) dimethylsilylenebis{1,1′-(2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(334) dimethylsilylenebis{1,1′-(2-propyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(335) dimethylsilylenebis{1,1′-(2-isopropyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(336) dimethylsilylenebis{1,1′-(2-phenyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(337) dimethylsilylenebis{1,1′-(2-trimethylsilylmethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(338) dimethylsilylenebis[1,1′-{2-methyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(339) dimethylsilylenebis[1,1′-{2-methyl-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(340) dimethylsilylenebis[1,1′-{2-ethyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconiumdichloride;

(341) dimethylsilylenebis[1,1′-{2-ethyl1-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl}]zirconium dichloride;

(342) dimethylsilylenebis{1,1′-(2-ethyl-4-phenyl-7-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(343) dimethylsilylenebis[1,1′-{2-ethyl-4-(1-naphthyl)-7-phenyl-4-hydroazulenyl}] zirconiumdichloride;

(344) dimethylsilylenebis[1,1′-{2-ethyl-4-(2-naphthyl)-7-phenyl-4-hydroazulenyl}] zirconiumdichloride;

(345) diphenylsilylenebis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(346) diphenylsilylenebis{1,1′-(2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(347) diphenylsilylenebis{1,1′-(2-propyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(348) diphenylsilylenebis{1,1′-(2-isopropyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(349) diphenylsilylenebis{1,1′-(2-phenyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(350) diphenylsilylenebis{1,1′-(2-trimethylsilylmethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(351) diphenylsilylenebis[1,1′-{2-ethyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconiumdichloride;

(352) diphenylsilylenebis[1,1′-{2-ethyl-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconiumdichloride;

(353) (methyl)(phenyl)silylenebis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl}] zirconiumdichloride;

(354) (methyl)(phenyl)silylenebis{1,1′-(2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(355) (methyl)(phenyl)silylenebis[1,1′-{2-ethyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconiumdichloride;

(356) (methyl)(phenyl)silylenebis[1,1′-{2-ethyl-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconiumdichloride;

(357) dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(358) dimethylsilylenebis{1,1′-(2-ethyl-4-phenyl-7-isopropyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(359) dimethylsilylenebis[1,1′-{2-ethyl-4-(1-naphthyl)-7-isopropyl-4,5,6,7,8-pentahydroazulenyl}]zirconium dichloride;

(360) dimethylsilylenebis[1,1′-{2-ethyl-4-(2-naphthyl)-7-isopropyl-4,5,6,7,8-pentahydroazulenyl}]zirconium dichloride;

(361) dimethylsilylene{1-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(362) dimethylsilylene{1-(2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(363) dimethylsilylene[1-{2-ethyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(364) dimethylsilylene[1-{2-ethyl-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(365) dimethylsilylene{1-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(366) dimethylsilylene{1-(2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(367) dimethylsilylene[1-{2-ethyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(368) dimethylsilylene[1-{2-ethyl-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(369) methylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(370) methylenebis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(371) methylene bis{1,1′-(2-methyl-6-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(372) methylenebis{1,1′-(2-ethyl-4,7-diisopropyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(373) methylene bis{1,1′-(4,6-dimethylcyclopentacyclooctenyl)} zirconiumdichloride;

(374) methylene bis{1,1′-(4-methyl-6-isopropylcyclopentacyclooctenyl)}zirconium dichloride;

(375) methylene bis{1,1′-(2-methyl-5-phenylcyclopentacyclooctenyl)}zirconium dichloride;

(376) ethylene bis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(377) ethylene bis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(378) ethylene bis{1,1′-(2-methyl-6-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(379) ethylenebis{1,1′-(2-ethyl-4,7-diisopropyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(380) ethylene bis{1,1′-(4,6-dimethylcyclopentacyclooctenyl)} zirconiumdichloride;

(381) ethylene bis{1,1′-(4-methyl-6-isopropylcyclopentacyclooctenyl)}zirconium dichloride;

(382) ethylene bis{1,1′-(2-methyl-5-phenylcyclopentacyclooctenyl)}zirconium dichloride;

(383) ethylene{(1-(2,4,7-trimethylindenyl)}{1-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(384) ethylene{(1-(2-ethyl-4,5-benzoindenyl)}{1-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(385) dimethylmethylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(386) dimethylmethylenebis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(387) dimethylmethylene bis{1,1′-(2-methyl-6-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(388) dimethylmethylenebis{1,1′-(2-ethyl-4,7-diisopropyl-4,5,6,7,8-pentahydroazulenyl)}zirconium dichloride;

(389) dimethylmethylene bis{1,1′-(4,6-dimethylcyclopentacyclooctenyl)}zirconium dichloride;

(390) dimethylmethylenebis{1,1′-(4-methyl-6-isopropylcyclopentacyclooctenyl)} zirconiumdichloride;

(391) dimethylmethylenebis{1,1′-(2-methyl-5-phenylcyclopentacyclooctenyl)} zirconiumdichloride;

(392) dimethylmethylene{(1-(2,4,7-trimethylindenyl)}{1-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(393) dimethylmethylene{(1-(2-ethyl-4,5-benzoindenyl)}{1-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(394) dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(395) dimethylsilylene bis{1,1′-(2-methyl-6-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(396) dimethylsilylenebis{1,1′-(2-ethyl-4,7-diisopropyl-4-hydroazulenyl)} zirconiumdichloride;

(397) dimethylsilylene bis{1,1′-(4,6-dimethylcyclopentacyclooctenyl)}zirconium dichloride;

(398) dimethylsilylenebis{1,1′-(4-methyl-6-isopropylcyclopentacyclooctenyl)} zirconiumdichloride;

(399) dimethylsilylenebis{1,1′-(2-methyl-5-phenylcyclopentacyclooctenyl)} zirconiumdichloride;

(400) dimethylsilylene{(1-(2,4,7-trimethylindenyl)}{1-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(401) dimethylsilylene{(1-(2-ethyl-4,5-benzoindenyl)}{1-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(402) (methyl)(phenyl)silylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(403) (methyl)(phenyl)silylenebis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(404) diphenylsilylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(405) tetramethyldisilylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(406) tetramethyldisilylenebis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(407) dimethylgermylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(408) dimethylgermylenebis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(409) dimethylsilylene bis{1,1′-(2-benzyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(410) dimethylsilylene bis{1,1′-(2-heptyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(411) dimethylsilylene bis{1,1′-{2-octyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(412) dimethylsilylenebis[1,1′-{2-(1-phenylethyl)-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(413) dimethylsilylenebis[1,1′-{2-(2-phenylethyl)-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(414) dimethylsilylenebis[1,1′-{2-(1-naphthyl)-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(415) dimethylsilylenebis[1,1′-(2-(2-naphthyl)-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(416) dimethylsilylenebis{1,1′-(2-dimethylphenylsilyl-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(417) dimethylsilylenebis[1,1′-{2-benzyl-4-(1-naphthyl)-4-hydroazulenyl)} zirconiumdichloride;

(418) dimethylsilylenebis[1,1′-{2-benzyl-4-(2-naphthyl)-4-hydroazulenyl)} zirconiumdichloride;

(419) dimethylsilylenebis{1,1′-(2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(420) dimethylsilylenebis{1,1′-(2-heptyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(421) dimethylsilylenebis{1,1′-(2-octyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(422) dimethylsilylenebis[1,1′-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(423) dimethylsilylenebis[1,1′-{2-(2-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(424) dimethylsilylenebis[1,1′-{2-(1-naphthyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(425) dimethylsilylenebis[1,1′-{2-(2-naphthyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(426) dimethylsilylenebis{1,1′-(2-dimethylphenylsilyl-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(427) dimethylsilylenebis[1,1′-{2-benzyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(428) dimethylsilylenebis[1,1′-{2-benzyl-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(429) diphenylsilylene bis{1,1′-(2-benzyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(430) diphenylsilylenebis[1,1′-{2-benzyl-4-(1-naphthyl)-4-hydroazulenyl)} zirconiumdichloride;

(431) diphenylsilylenebis[1,1′-{2-benzyl-4-(2-naphthyl)-4-hydroazulenyl)} zirconiumdichloride;

(432) diphenylsilylenebis{1,1′-(2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(433) diphenylsilylenebis[1,1′-{2-(1-phenylethyl)-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(434) diphenylsilylenebis[1,1′-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(435) (methyl)(phenyl)silylenebis{1,1′-(2-benzyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(436) (methyl)(phenyl)silylenebis[1,1′-{2-benzyl-4-(1-naphthyl)-4-hydroazulenyl)} zirconiumdichloride;

(437) (methyl) (phenyl)silylenebis[1,1′-{2-benzyl-4-(2-naphthyl)-4-hydroazulenyl)} zirconiumdichloride;

(438) (methyl)(phenyl)silylenebis{1,1′-(2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride;

(439) (methyl)(phenyl)silylenebis[1,1′-{2-(1-phenylethyl)-4-phenyl-4-hydroazulenyl)} zirconiumdichloride;

(440) (methyl)(phenyl)silylenebis[1,1′-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)}zirconium dichloride;

(441) dimethylsilylene {1-(2-benzyl-4-phenyl-4-hydroazulenyl)}{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(442) dimethylsilylene [1-{2-benzyl-4-(1-naphthyl)-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(443) dimethylsilylene [1-{2-benzyl-4-(2-naphthyl)-4-hydroazulenyl)]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(444) dimethylsilylene[1-(2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(445) dimethylsilylene [1-{2-(1-phenylethyl)-4-phenyl-4-hydroazulenyl}]{1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;

(446) dimethylsilylene[1-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl -4,5-benzoindenyl)} zirconium dichloride;

(447) dimethylsilylene {1-(2-benzyl-4-phenyl-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(448) dimethylsilylene [1-{2-benzyl-4-(1-naphthyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(449) dimethylsilylene [1-{2-benzyl-4-(2-naphthyl)-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(450) dimethylsilylene[1-{2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(451) dimethylsilylene [1-{2-(1-phenylethyl)-4-phenyl-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(452) dimethylsilylene[1-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl}]{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(453) 9-silafluorene-9,9-diylbis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(454) 9-silafluorene-9,9-diylbis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(455) 9-silafluorene-9,9-diylbis{1,1′-(2,8-dimethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(456) 9-silafluorene-9,9-diylbis{1,1′-{2-methyl-4-(1-naphthyl)-4-hydroazulenyl}] zirconiumdichloride;

(457) 9-silafluorene-9,9-diyl {1-(2-methyl-4-phenyl-4-hydroazulenyl)}{1-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(458) 9-silafluorene-9,9-diyl {1-(2-methyl-4-phenyl-4-hydroazulenyl)}{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(459) 1-silaindene-1,1-diylbis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(460) 1-silaindene-1,1-diyl bis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride;

(461) 1-silaindene-1,1-diylbis{1,1′-(2,8-dimethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(462) 1-silaindene-1,1-diylbis[1,1′-{2-methyl-4-(1-naphthyl)-4-hydroazulenyl}] zirconiumdichloride;

(463) 1-silaindene-1,1-diyl {1-(2-methyl-4-phenyl-4-hydroazulenyl)}{1-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(464) 1-silaindene-1,1-diyl {1-(2-methyl-4-phenyl-4-hydroazulenyl)}{1-(2-methyl-4-phenylindenyl)} zirconium dichloride;

(465) tetramethyl-1-silacyclopentadiene-1,1-diylbis(1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(466) tetramethyl-1-silacyclopentadiene-1,1-diylbis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(467) tetramethyl-1-silacyclopentadiene-1,1-diylbis{1,1′-(2,8-dimethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(468) tetramethyl-1-silacyclopentadiene-1,1-diylbis[1,1′-{2-methyl-4-(1-naphthyl)-4-hydroazulenyl}] zirconiumdichloride; (469) tetramethyl-1-silacyclopentadiene-1,1-diyl{1-(2-methyl-4-phenyl-4-hydroazulenyl)}{1-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(470) tetramethyl-1-silacyclopentadiene-1,1-diyl{1-(2-methyl-4-phenyl-4-hydroazulenyl)} {1-(2-methyl-4-phenylindenyl)}zirconium dichloride;

(471) 1-silacyclo-3-pentene-1,1-diylbis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(472) 1-silacyclo-3-pentene-1,1-diylbis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(473) 1-silacyclo-3-pentene-1,1-diylbis{1,1′-(2,8-dimethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;

(474) 1-silacyclo-3-pentene-1,1-diylbis[1,1′-{2-methyl-4-(1-naphthyl)-4-hydroazulenyl}] zirconiumdichloride;

(475) 1-silacyclo-3-pentene-1,1-diyl{1-(2-methyl-4-phenyl-4-hydroazulenyl)}{1-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconiumdichloride;

(476) 1-silacyclo-3-pentene-1,1-diyl{1-(2-methyl-4-phenyl-4-hydroazulenyl)} {1-(2-methyl-4-phenylindenyl)}zirconium dichloride.

In addition, as the transition metal compounds according to the presentinvention, there can also be exemplified those compound in which one orboth of two chlorine atoms constituting the groups X and Y in thegeneral formulae (I) to (VI) are substituted by a hydrogen atom, afluorine atom, bromine atom, an iodine atom, a methyl group, a phenylgroup, a fluorophenyl group, a benzyl group, an methoxy group, adimethylamino group, a diethylamino group, or the like. Further, therecan also be exemplified those compounds in which zirconium as thecentral metal M of each of the above-mentioned compounds, is substitutedby titanium, hafnium, tantalum, niobium, vanadium, tungsten, molybdenumor the like. Among them, compounds containing Group 4 transition metalssuch as zirconium, titanium or hafnium are preferred, and compoundscontaining zirconium or hafnium are especially preferred.

Next, the catalyst (1) for polymerization of α-olefin according to thefirst aspect of the present invention is explained below. The catalyst(1) comprises, as essential components, the afore-mentioned transitionmetal compound (component A) and the specific ion exchangeable layercompound or the inorganic silicate (component B), and as an optionalcomponent, the organoaluminum compound (component C).

First, as the component B, the inorganic silicate or the ionexchangeable layer compound except for silicate (hereinafter referred tomerely as “ion exchangeable layer compound”) is described in detailbelow.

As the afore-mentioned ion exchangeable layer compounds as the component(B), there can be exemplified ionic crystalline compounds of a hexagonalclosest packing type, an antimony type, a CdCl₂ type or a CdI₂ type,which have a layer crystal structure. Specific examples of the ionexchangeable layer compounds may include crystalline acid salts ofpolyvalent metals such as α-Zr(HAsO₄)₂.H₂O, α-Zr(HPO₄)₂,α-Zr(KPO₄)₂.3H₂O, α-Ti (HPO₄)₂, α-Ti (HAsO₄)₂.H₂O, α-Sn(HPO₄)₂.H₂O,γ-Zr(HPO₄)₂, γ-Ti(HPO₄)₂ or γ-Ti(NH₄PO₄)₂·H₂O.

The afore-mentioned ion exchangeable layer compounds may be treated withsalts and/or acids, if required. The ion exchangeable layer compoundsexcept for silicates which are treated with neither salts nor acids,have such a crystal structure that layers formed by ionic bond or thelike are overlapped in parallel to one another with a weak bonding forcetherebetween and, therefore, the layers contain ions exchangeable witheach other.

As the afore-mentioned inorganic silicates as the component (B), therecan be exemplified clays, clay minerals, zeolite, diatomaceous earth orthe like. These inorganic silicates may be either synthesized productsor naturally outputted minerals. Specific examples of clays or clayminerals may include allophane group clays or clay minerals such asallophane; kaolin group clays or clay minerals such as dickite, nacrite,kaolinite or anauxite, halloysite group clays or clay minerals such asmeta-halloysite or halloysite; serpentine group clays or clay mineralssuch as chrysotile, lizardite or antigorite; smectite group clays orclay minerals such as montmorillonite, sauconite, beidellite,nontronite, saponite or hectorite; vermiculite minerals such asvermiculite; mica minerals such as illite, sericite or glauconite;attapulgite; sepiolite; palygorskite; bentonite; gnarl clay; gairomeclay hisingerite; pyrophyllite; chlorite groups; or the like. Theseinorganic silicates may be in the form of mixed layers thereof. Inaddition, as the synthetic inorganic silicates, there can be exemplifiedsynthetic mica, synthetic hectorite, synthetic saponite, synthetictaeniolite or the like.

Among the afore-mentioned inorganic silicates, kaolin group clays orclay minerals, halloysite group clays or clay minerals, serpentine groupclays or clay minerals, smectite group clays or clay minerals,vermiculite minerals, mica minerals, synthetic mica, synthetichectorite, synthetic saponite or synthetic taeniolite are preferred, andespecially preferred inorganic silicates are smectite, vermiculiteminerals, synthetic mica, synthetic hectorite, synthetic saponite andsynthetic taeniolite. These inorganic silicates may be used in untreatedstate as they are, or may be used after subjected to treatments such ascrushing by a ball mill, screening or the like. Further, these inorganicsilicates may be used singly or in the form of a mixture of any two ormore thereof.

The afore-mentioned ion exchangeable layer compounds except forsilicates and the inorganic silicates as the component (B) can betreated with salts and/or acids to control an acid strength of thesesolid compounds. Further, when these compounds are treated with salts,ion composites, molecule composites or organic derivatives are formed,so that it becomes possible to appropriately change the surface area andinterlayer distance thereof. Specifically, exchangeable ions existingbetween the respective layers can be replaced with other bulkier ions bythe aid of ion exchanging properties of these compounds, therebyobtaining a layer substance having an increased interlayer distance.

If these compounds are not pre-treated as described above, it ispreferred that metal cations contained therein are ion-exchanged withcations dissociated from the below-mentioned salts and/or acids.

The salts used for the afore-mentioned ion exchange, may be compoundscomprising a cation which contains at least one atom selected from thegroup consisting of Group 1-14 atoms, preferably compounds comprising acation which contains at least one atom selected from the groupconsisting of Group 1-14 atoms and at least one anion derived from anatom or atomic group selected from the group consisting of halogenatoms, inorganic acids and organic acids, more preferably compoundscomprising a cation which contains at least one atom selected from thegroup consisting of Group 2-14 atoms and at least one anion selectedfrom the group consisting of Cl, Br, I, F, PO₄, SO₄, NO₃, CO₃, C₂O₄,ClO₄, OOCCH₃, CH₃COCHCOCH₃, OCl₂, O(NO₃)₂, O(ClO₄)₂, O(SO₄), OH, O₂Cl₂,OCl₃, OOCH and OOCCH₂CH₃. These salts may be used singly or in the formof a mixture of any two or more thereof in combination.

The acids used for the aforementioned ion exchange, may be selected fromhydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalicacid. These acids may be used singly or in the form of a mixture of anytwo or more thereof. The salt treatment can be used in combination withthe acid treatment. As methods in which the salt treatment and the acidtreatment are used in combination, there can be exemplified a method ofconducting the acid treatment after the salt treatment, a method ofconducting the salt treatment after the acid treatment, a method ofconducting the salt and acid treatments simultaneously, and a method ofconducting the salt and acid treatments simultaneously after the salttreatment. Incidentally, the acid treatment has such effects,afore-mentioned ion exchange that impurities can be removed from thesurface of the component (B), and that a part of cations contained inthe crystal structure such as Al, Fe, Mg or Li can be eluted therefrom.

The treating conditions used for the salt or acid treatment are notparticularly restricted. However, it is suitable that the concentrationof the salt or acid is usually in the range of 0.1 to 30% by weight; thetreating temperature is usually from room temperature to a boiling pointof solvent used; and the treating time is usually from 5 minutes to 24hours, such that at least a part of the compound to be treated is solvedout. Further, the salts and the acids are usually used in the form of anaqueous solution.

In the afore-mentioned salt and/or acid treatments, the component (B)may be pulverized or granulated before, during or after the salt and/oracid treatments to control the shape thereof. In addition, otherchemical treatments such as alkali treatment or treatments by organicsubstances may be used in combination. The thus-prepared component (B)has preferably a pore volume of usually not less than 0.1 cc/g, morepreferably 0.3 to 5 cc/g, when measured with respect to pores having aradius of not less than 20 Å by a mercury-penetrating method. Such acomponent (B) generally contains an absorbed water or an interlayerwater. Here, the absorbed water means water absorbed on a surface or acrystal fracture face of the ion exchangeable layer compound or theinorganic silicate, and the interlayer water means water existingbetween the layers.

In accordance with the present invention, it is preferred that thecomponent (B) is used after removal of the afore-mentioned absorbedwater or interlayer water. The methods for removing the water, are norparticularly restricted, but there can be used dehydrating methods suchas heating, heating in the presence of a flowing gas, heating under areduced pressure, azeotropy with an organic solvent, or the like. Theheating may be conducted at such a temperature that no absorbed waterand interlayer water exists in the component (B). The heatingtemperature is usually not less than 100° C., preferably not less than150° C. However, the use of such a high temperature which causesdestruction of the crystal structure should be avoided. The heating timeis usually not less than 0.5 hour, preferably not less than one hour.The weight loss of the thus-treated component (B) is preferably not morethan 3% by weight, when the suction is conducted at a temperature of200° C. under a pressure of 1 mm Hg for 2 hours. In accordance with thepresent invention, in the case where the component (B) whose weight lossis adjusted to not more than 3% by weight based on the weight of thecomponent (B) is used, it is preferred that the weight loss of thecomponent (B) is also maintained when the component (B) is brought intocontact with the essential component (A) and the below-mentionedoptional component (C).

Next, the organoaluminum compound (component (C)) is explained in detailbelow. As the component (C), there can be preferably used organoaluminumcompounds represented by the general formula (VII):

AlR_(a)P_(3-a)  (VII)

wherein R is a hydrocarbon group having 1 to 20 carbon atoms; P is ahydrogen atom, a halogen atom, an alkoxy group or a siloxy group; and“a” is a number satisfying 0<a≦3.

Specific examples of the organoaluminum compounds represented by theafore-mentioned general formula (VII) may include trialkylaluminums suchas trimethylaluminum, triethylaluminum, tripropylaluminum ortriisobutylaluminum, halogen-containing or alkoxy-containingalkylaluminums such as diethylaluminum monochloride or diethylaluminummonomethoxide, or the like. Among them, trialkylaluminums can bepreferably used. Further, in the case of the catalyst (1) forpolymerization of α-olefin according to the first aspect of the presentinvention, aluminoxanes such as methylaluminoxane or the like can alsobe used as the component (C).

The catalyst (1) for polymerization of α-olefin can be prepared bybringing the essential components (A) and (B) and the optional component(C) in contact with each other. The contacting method is notparticularly restricted, but the following methods (i) to (v) can beexemplified. Incidentally, the contact between these components may beperformed not only upon the production of the catalyst but also uponpre-polymerization or polymerization of the olefins.

(i) Method of bringing the components (A) and (B) into contact with eachother;

(ii) Method of bringing the components (A) and (B) into contact witheach other and then adding the component (C) to the mixture;

(iii) Method of bringing the components (A) and (C) into contact witheach other and then adding the component (B) to the mixture;

(iv) Method of bringing the components (B) and (C) into contact witheach other and then adding the component (A) to the mixture; and

(v) Method of bringing the components (A), (B) and (C) into contact witheach other at the same time.

When or after the respective components are brought into contact witheach other, polymers such as polyethylene or polypropylene or solidcomponents of inorganic oxides such as silica or alumina may co-existtherein or may be contacted therewith.

In addition, the contact between the respective components can beconducted in an atmosphere of an inert gas such as nitrogen or in thepresence of an inert hydrocarbon solvent such as pentane, hexane,heptane, toluene or xylene. Further, the contact is preferably conductedat a temperature of from −20° C. to a boiling point of the solvent used,more preferably from room temperature to the boiling point of thesolvent used.

The amount of the component (A) used is usually in the range of 10⁻⁴ to10 mmol, preferably 10⁻³ to 5 mmol based on one gram of the component(B). The amount of the component (C) used is usually in the range of0.01 to 10⁴ mmol, preferably 0.1 to 100 mmol based on one gram of thecomponent (B). In addition, the atomic ratio of the transition metalcontained in the component (A) to aluminum contained in the component(C) is usually in the range of 1/0.01 to 1/10⁶, preferably 1/0.1 to1/10⁵. The thus-prepared catalyst may be used as it is without washing,or may be used after washing. Further, the catalyst can be used incombination with a further component (C′) which is composed of similarcompounds to the component (C), if required. That is, when thecomponents (A) and/or (B) and the component (C) are used to prepare thecatalyst, the further component (C′) may be added to a reaction systemseparately from that the component (C) used for the preparation of thecatalyst. In this case, the amount of the further added component (C′)can be selected such that the atomic ratio of the transition metalcontained in the component (A) to aluminum contained in the furtheradded component (C′) is 1/0 to 1/10⁴.

Next, the catalyst (2) for polymerization of α-olefin according to thesecond aspect of the present invention, is explained in detail below.The catalyst (2) may contain, as essential components, (i) a noveltransition metal compound represented by the afore-mentioned generalformula (II), (III), (IV), (V) or (VI) (component (A)) and (ii) analuminumoxy compound, an ionic compound capable of reacting with thecomponent (A) to convert the component (A) into a cation or a Lewis acid(component (D)), and as an optional component, (iii) a fine particlecarrier (component (E)). Incidentally, some of Lewis acids can act asthe ionic compound capable of reacting with the component (A) to convertthe component (A) into a cation. Accordingly, if the afore-mentionedcompound having the properties of both the Lewis acid and the ioniccompound is used, the compound is regarded as belonging to any onethereof.

As the aforementioned aluminumoxy compounds, there can be exemplifiedthose compounds represented by the following general formulae (VIII),(IX) and (X):

In the afore-mentioned general formulae (VIII), (IX) and (X), R⁹ is ahydrogen atom or a hydrocarbon group having preferably 1 to 10 carbonatoms, more preferably 1 to 6 carbon atoms, providing that when aplurality of the R⁹ are present in the same molecule, these R⁹ may bethe same or different; and p is an integer of 0 to 40, preferably 2 to30.

The compounds represented by the general formulae (VIII) and (IX) arealso called “alumoxane”, and can be obtained by reacting at least onetrialkylaluminum with water. Specific examples of the compoundsrepresented by the general formulae (VIII) and (IX) may include (i)compounds obtained by reacting one kind of trialkylaluminum with water,such as methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxaneor isobutylalumoxane, (ii) compounds obtained by reacting two kinds oftrialkylaluminum with water, such as methylethylalumoxane,methylbutylalumoxane or methylisobutylalumoxane, or the like. Amongthem, methylalumoxane and methylisobutylalumoxane are preferred.

The afore-mentioned alumoxanes can be used in combination within eachgroup or between a plurality of groups. The alumoxanes can be preparedunder various known conditions. Specifically, the following methods canbe used for the production of these alumoxanes:

(a) Method of directly reacting trialkylaluminum with water in thepresence of an appropriate organic solvent such as toluene, benzene orether;

(b) Method of reacting trialkylaluminum with a salt containingcrystallization water, e.g., a hydrate of copper sulfate or aluminumsulfate;

(c) Method of reacting trialkylaluminum with a water content impregnatedin silica gel or the like;

(d) Method of mixing trimethylaluminum and triisobutylaluminum together,and then directly reacting the mixed trialkylaluminums with water in thepresence of an appropriate organic solvent such as toluene, benzene orether;

(e) Method of mixing trimethylaluminum and triisobutylaluminum together,and then reacting the mixed trialkylaluminums with a salt containingcrystallization water, e.g., a hydrate of copper sulfate or aluminumsulfate while heating;

(f) Method of impregnating water into silica gel or the like, andtreating the water-impregnated silica gel, etc., withtriisobutylaluminum and then with trimethylaluminum;

(g) Method of preparing methylalumoxane and isobutylalumoxane by a knownmethod, and then mixing these two components together at a predeterminedratio to be reacted with each other while heating; and

(h) Method of adding a salt containing crystallization water such ascopper sulfate pentahydrate and trimethylaluminum into an aromatichydrocarbon solvent such as benzene or toluene and reacting thesecomponents with each other at a temperature of about −40° C. to about40° C.

The molar ratio of water used to the trimethylaluminum is usually in therange of 0.5 to 1.5. Methylalumoxane prepared by the afore-mentionedmethods is a linear or cyclic organoaluminum polymer.

The compounds represented by the general formula (X) can be obtained byreacting at least one trialkylaluminum with alkyl boric acid representedby the following general formula (XI) at a molar ratio of 10:1 to 1:1.

R¹⁰—B—(OH)₂  (XI)

wherein R¹⁰ is a hydrocarbon group or a halogenated hydrocarbon groupboth having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

Specific examples of the compounds represented by the general formula(XI) may include the following reaction products:

(a) Reaction products obtained by reacting trimethylaluminum withmethylboric acid at a molar ratio of 2:1;

(b) Reaction products obtained by reacting triisobutylaluminum withmethylboric acid at a molar ratio of 2:1;

(c) Reaction products obtained by reacting trimethylaluminum,triisobutylaluminum and methylboric acid with each other at a molarratio of 1:1:1;

(d) Reaction products obtained by reacting trimethylaluminum withethylboric acid at a molar ratio of 2:1; and

(e) Reaction products obtained by reacting triethylaluminum withbutylboric acid at a molar ratio of 2:1.

In addition, as the ionic compounds capable of reacting with thecomponent (A) to convert the component (A) into a cation, there can beexemplified those compounds represented by the general formula (XII):

[K]e⁺[Z]e⁻  (XII)

In the general formula (XII), K represents a cationic component.Examples of the cations may include carbonium cation, tropylium cation,ammonium cation, oxonium cation, sulfonium cation, phosphonium cation orthe like. Further, metal cations which tend to be reduced per se,cations of organic metals or the like can also be used.

Specific examples of the afore-mentioned cations may include triphenylcarbonium, diphenyl carbonium, cyclohepta trienium, indenium,triethylammonium, tripropylammonium, tributylammonium, N,N-dimethylammonium, dipropylammonium, dicyclohexylammonium,triphenylphosphonium, trimethylphosphonium,tris(dimethylphenyl)phosphonium, tris(methylphenyl)phosphonium,triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silverion, gold ion, platinum ion, copper ion, palladium ion, mercury ion,ferrocenium ion or the like.

In the general formula (XII), Z represents an ionic anion component(generally a non-coordinated component), which constitutes a counteranion against the cation produced by the conversion of the component(A). As the anion Z, there can be exemplified anions of organic boroncompounds, anions of organoaluminum compounds, anions of organogalliumcompounds, anions of organophosphorus compounds, anions of organoarseniccompounds, anions of organoanthimony compounds or the like. Specificexamples of these organic compounds are as follows.

(a) tetraphenylboron, tetrakis(3,4,5-trifluorophenyl)boron,tetrakis{3,5-bis(trifluoromethyl)phenyl}boron,tetrakis{3,5-di(t-butyl)phenyl}boron, tetrakis(pentafluorophenyl)boron,or the like;

(b) tetraphenylaluminum, tetrakis(3,4,5-trifluorophenyl) aluminum,tetrakis{3,5-bis(trifluoromethyl)phenyl}aluminum,tetrakis(3,5-di(t-butyl)phenyl)aluminum,tetrakis(pentafluorophenyl)aluminum, or the like;

(c) tetraphenylgallium, tetrakis(3,4,5-trifluorophenyl)gallium,tetrakis{3,5-bis(trifluoromethyl)phenyl)gallium,tetrakis(3,5-di(t-butyl)phenyl)gallium,tetrakis(pentafluoro)phenylgallium, or the like;

(d) tetraphenyl phosphorus, tetrakis (pentafluorophenyl) phosphorus, orthe like;

(e) tetraphenyl arsenic, tetrakis(pentafluorophenyl) arsenic, or thelike;

(f) tetraphenyl antimony, tetrakis(pentafluorophenyl) antimony, or thelike; and

(g) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate,or the like.

Further, as the Lewis acids, especially those capable of converting thecomponent (A) into a cation, there can be exemplified variousorganoboron compounds, halogenated metal compounds, solid acids or thelike. Specific examples of these Lewis acids are as follows:

(a) organoboron compounds such as triphenylboron,tris(3,5-difluorophenyl)boron or tris(pentafluorophenyl)boron;

(b) halogenated metal compounds such as aluminum chloride, aluminumbromide, aluminum iodide, magnesium chloride, magnesium bromide,magnesium iodide, magnesium chloride bromide, magnesium chloride iodide,magnesium bromide iodide, magnesium chloride hydride, magnesium chloridehydroxide, magnesium bromide hydroxide, magnesium chloride alkoxide ormagnesium bromide alkoxide; and

(c) solid acids such as alumina or silica-alumina.

In the catalyst (2) for polymerization of α-olefin, the fine particlecarrier as the optional component (E) may be composed of an inorganic ororganic compound, and in the form of granules or particles having aparticle diameter of usually 5 μm to 5 mm, preferably 10 μm to 2 mm.

As the afore-mentioned inorganic carrier, there can be exemplifiedoxides such as SiO₂, Al₂O₃, MgO, ZrO, TiO₂, B₂O₃ or ZnO; compositeoxides such as SiO₂—MgO, SiO₂—Al₂O₃, SiO₂—TiO₂, SiO₂—Cr₂O₃ orSiO₂—Al₂O₃—MgO; or the like.

As the afore-mentioned organic carrier, there can be exemplified fineparticles of porous polymers, for example, polymers or copolymers ofα-olefins having 2 to 14 carbon atoms such as ethylene, propylene,1-butene or 4-methyl-1-pentene; polymers or copolymers of aromaticunsaturated hydrocarbons such as styrene or divinylbenzene; or the like.These organic carriers have a specific surface area of usually 20 to1,000 m²/g, preferably 50 to 700 m²/g, and a pore volume of usually notless than 0.1 cm³/g, preferably not less than 0.3 cm³/g, more preferablynot less than 0.8 cm³/g.

The catalyst (2) for polymerization of α-olefin may contain, as otheroptional components than the fine particle carrier, for example, proticcompounds such as H₂O, methanol, ethanol or butanol; electron donativecompounds such as ethers, esters or amines; alkoxy-containing compoundssuch as phenylborate, dimethylmethoxyaluminum, phenylphosphite,tetraethoxysilane or diphenyldimethosilane; or the like.

As still further optional components other than the afore-mentionedcompounds, there can be exemplified tri lower-alkylaluminums such astrimethylaluminum, triethylaluminum or triisobutylaluminum;halogen-containing alkylaluminums such as diethylaluminum chloride,diisobutylaluminum chloride or methylaluminum sesqui-chloride;alkylaluminum hydrides such as diethylaluminum hydride;alkoxy-containing alkylaluminums such as diethylaluminum ethoxide ordimethylaluminum butoxide; aryloxy-containing alkylaluminums such asdiethylaluminum phenoxide; or the like.

In the catalyst (2) for polymerization of α-olefin, the aluminum-oxycompound, the ionic compound capable of reacting with the component (A)to convert the component (A) into a cation, and the Lewis acid as thecomponent (D) are used singly or in the form of a mixture of any two ormore thereof in combination. Incidentally, it is preferred that as thestill further optional components, one or more kinds of theafore-mentioned lower-alkylaluminum, halogen-containing alkylaluminum,alkylaluminum hydride, alkoxy-containing alkylaluminum oraryloxy-containing alkylaluminum are contained in the catalyst (2) forpolymerization of α-olefin, together with the aluminum-oxy compound, theionic compound or the Lewis acid.

The catalyst (2) for polymerization of α-olefin may be prepared bybringing the components (A) and (D) into contact with each other insideor outside of a polymerization vessel and in the presence or absence ofa monomer to be polymerized. In this case, the components (A) and (D),and if required, the component (E), etc., may be introduced separatelyinto the polymerization vessel. Alternatively, the components (A) and(D) may be introduced into the polymerization vessel after both thecomponents have been preliminarily brought into contact with each other.Further, after the components (A) and (D) are mixed together andimpregnated into the component (E), the mixture may be introduced intothe polymerization vessel.

The contact between the respective components can be conducted in anatmosphere containing an inert gas such as nitrogen or in the presenceof an inert hydrocarbon solvent such as pentane, hexane, heptane,toluene or xylene. In addition, the contact can be conducted at atemperature of from −20° C. to a boiling point of the solvent used,preferably from room temperature to the boiling point of the solventused. The thus-produced catalyst may be used as it is without washing,or may be used after washing. Further, the obtained catalyst may be usedin combination with additional components, if required.

Also, when the components (A), (D) and (E) are preliminarily broughtinto contact with each other, the contact can be performed in thepresence of the monomer to be polymerized, i.e., α-olefin to partiallypolymerize the α-olefin (so-called pre-polymerization). Morespecifically, before the polymerization, the α-olefin such as ethylene,propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene,3-methyl-1-butene, vinylcycloalkanes or styrene is pre-polymerized andwashed, if required. The thus-produced pre-polymerization product can beused as a catalyst. In this case, it is preferred that thepre-polymerization is conducted in the presence of an inert solventunder such a moderate reaction condition that the polymer is produced inan amount of usually 0.01 to 1,000 g, preferably 0.1 to 100 g based onone gram of the solid catalyst.

The amounts of the components (A) and (D) used are optional. Forexample, in the case of solution polymerization, the amount of thecomponent (A) used is usually in the range of 10⁻⁷ to 10² mmol/liter(calculated as the transition metal), preferably 10⁻⁴ to 1 mmol/liter.In the case where the aluminum-oxy compound is used as the component(D), the molar ratio of 1 to the transition metal is usually in therange of 10 to 10⁵, preferably 100 to 2×10⁴, more preferably 100 to 10⁴.On the other hand, in the case where the ionic compound or the Lewisacid is used as the component (D), the molar ratio of the ionic compoundor the Lewis acid to the transition metal is usually in the range of 0.1to 1,000, preferably 0.5 to 100, more preferably 1 to 50.

Next, the method for producing an α-olefin polymer according to thepresent invention, is explained in detail below. In accordance with thepresent invention, the afore-mentioned catalyst and α-olefin are broughtinto contact with each other to polymerize or copolymerize the α-olefin.The catalyst for polymerization of α-olefin according to the presentinvention can be applied to not only a solution polymerization using asolvent, but also a liquid-phase non-solvent polymerization usingsubstantially no solvent, a gas-phase polymerization or a meltpolymerization. These polymerizations can be conducted either in acontinuous manner or in a batch manner.

As the solvents used for the solution polymerization, there can beexemplified inert saturated aliphatic or aromatic hydrocarbons such ashexane, heptane, pentane, cyclohexane, benzene or toluene. Thesesolvents can be used singly or in the form of a mixture of any two ormore thereof. The polymerization temperature is usually in the range of−78° C. to 250° C., preferably −20° C. to 100° C. The olefin pressure inthe reaction system is not particularly restricted, but preferably fromordinary pressure to 2,000 kgf /cm²G (Geuge), more preferably fromordinary pressure to 50 kgf/cm²G. Further, the molecular weight of theresultant α-olefin polymer can be controlled by known methods such asappropriate selection of reaction temperature and reaction pressure usedor introduction of hydrogen.

As the raw α-olefins, there can be used α-olefins having usually 2 to 20carbon atoms, preferably 2 to 10 carbon atoms. Specific examples of theα-olefins may include ethylene, propylene, 1-butene, 4-methyl-1-pentene,1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene or the like. The catalyst according to thepresent invention can be preferably applied to stereoregulatedpolymerization of α-olefins having 3 to 10 carbon atoms, especially tothe polymerization of propylene.

Further, the catalyst according to the present invention can be appliedto not only homopolymerization or copolymerization of theafore-mentioned α-olefins, but also copolymerization of the α-olefinswith the other monomers. As the other monomers copolymerizable with theα-olefins, there can be exemplified conjugated dienes or non-conjugateddienes such as butadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene,1,8-nonadiene or 1,9-decadiene; cyclic olefins such as cyclopropene,cyclobutene, cyclopentene, norbornene or dicyclopentadiene; or the like.The polymerization or copolymerization of the α-olefins can be performedin multiple stages whose reaction conditions are different from eachother, i.e., in a manner of so-called multi-step polymerization, forexample, block copolymerization comprising pre-polymerization ofpropylene and copolymerization of ethylene with the polypropyreneprepared by the said pre-polymerization.

As described above, in accordance with the polymerization methodaccording to the present invention, there can be obtained an α-olefinpolymer which has a narrow molecular weight distribution and a narrowcomposition distribution, is excellent in transparency and mechanicalstrength and exhibits a good flowability.

Also, in the case where the polymerization of propylene was conducted byusing the catalyst according to the present invention, there can beobtained a crystalline polypropylene which can show a high value [mmmm](e.g., not less than 90%) and a unique regio defect amount:2,1-inversion of 0.5 to 2.0 mol % and 1,3-insertion of 0.06 to 0.40 mol%. The regio defect amount can be calculated according to the followingformula:

2,1-insertion percentage (%)=(Y/X)×1,000×1/5,

1,3-insertion percentage (%)=(Z/X)×1,000×1/5,

X=sum of integrated values from 27 ppm to 48 ppm,

Y=(A{circle around (1)}+A{circle around (2)}+A{circle around(3)}+A{circle around (4)}+A{circle around (5)}+A{circle around (6)})/6,

Z=(A{circle around (7)}+A{circle around (8)}+A{circle around (9)})/6

In the above formulae, A{circle around (1)}, A{circle around (2)},A{circle around (3)}, A{circle around (4)}, A{circle around (5)},A{circle around (6)}, A{circle around (7)}, A{circle around (8)} andA{circle around (9)} are areas at 42.3 ppm, 35.9 ppm, 38.6 ppm, 30.6ppm, 36.0 ppm, 31.5 ppm, 31.0 ppm, 37.2 ppm and 27.4 ppm, respectively,and indicate ratios between quantities of carbon atoms existing atrespective positions of the following partial structures (I) and (II):

In addition, in accordance with the present invention, there can beprovided novel transition metal compounds. Especially, in the case wherethe catalyst containing the transition metal compound represented by thegeneral formulae (II)-(VI) according to the present invention is used,the α-olefin polymer which is free from reduction of its molecularweight and deterioration of its stereo regularity, can show a highmolecular weight and a high melting point, and therefore, is applicableto extrusion molding or injection molding, can be produced with a highyield. The reason therefor is considered as follows, though not exactlyknown.

That is, in the novel transition metal compound represented by thegeneral formulae (II) and (III), since the groups R³ and R⁶ each form acondensed ring having not less than 7 members, the substituent groups R⁷and R⁸ bonded thereto take such a spatial arrangement as inclined at acertain angle relative to a plane of the condensed ring constituted bythe 5-membered ring and the R³ or R⁶. In addition, the substituentgroups R⁷ and R⁸ contain halogen atom(s) which is spatially bulkier thana hydrogen atom. The halogen atom acts to provide an appropriate sterichindrance and an appropriate configuration which cannot be achieved onlyby the hydrocarbon. As a result, effects of regulating the direction ofgrowth of polymer chains and the direction of coordination of monomersare enhanced, thereby improving the stereo regularity of the obtainedpolymers and further increasing the melting point thereof.

Further, it is considered that the halogen atom exerts an electroniceffect on centrally located metals, e.g., zirconium or hafnium, and theelectronic effect and the afore-mentioned stereostructure caneffectively prevent the chain transfer reaction, thereby increasing amolecular weight of the obtained polymer. Furthermore, since the 7- to10-membered ring formed by the groups R³ or R⁶ has double bond(s), themovement of the substituent groups R⁷ and R⁸ is inhibited andconfiguration of the ligands is firmly fixed. For this reason, it isconsidered that even if the polymerization temperature is increased, thesubstituent groups R⁷ and R⁸ do not lose the effects of regulating thedirection of growth of polymer chains and the direction of coordinationof monomers, thereby obtaining a high-molecular weight polymer having anexcellent stereo regularity.

In the novel transition metal compound represented by the generalformula (IV), since the substituent group R⁶ forms a condensed ringhaving not less than 7 members, the substituent group R⁸ bonded theretohas such a spatial arrangement as inclined at a certain angle relativeto a plane of the condensed ring constituted by the 5-membered ring andthe R⁶. In addition, the substituent group R⁸ is present at a β- orremoter position on R⁶ with respect to the 5-membered ring. Theseconditions allow the transition metal compound to have a spatiallybulkier structure, thereby imparting an appropriate steric hindrance andan appropriate configuration thereto. As a result, the same effects asgiven by the transition metal compound of the general formula (II) canbe obtained.

In the novel transition metal compound represented by the generalformula (V), since the substituent group R³ and R⁶ forms a condensedring having not less than 7 members, the substituent group R⁷ and R⁸bonded thereto has such a spatial arrangement as inclined at a certainangle relative to a plane of the condensed ring constituted by the5-membered ring and the R³ or R⁶. In addition, bulkier R¹ and R⁴ arebonded to the 5-membered ring. These conditions allow the transitionmetal compound to have a spatially bulkier structure, thereby impartingan appropriate steric hindrance and an appropriate configurationthereto. As a result, the same effects as provided by the transitionmetal compound of the general formula (II) can be obtained.

Further, in the novel transition metal compound represented by thegeneral formula (VI), since the groups R³ and R⁶ each form a condensedring having not less than 7 members, the substituent groups R⁷ and R⁸bonded thereto have such a spatial arrangement as inclined at a certainangle relative to a plane of the condensed ring constituted by the5-membered ring and the R³ or R⁶. In addition, the cyclic substituentgroup A is bonded to the cross-linking group Q. These conditions allowthe transition metal compound to have a spatially bulkier structure,thereby imparting an appropriate steric hindrance and an appropriateconfiguration thereto. As a result, the same effects as provided by thetransition metal compound of the general formula (II) can be obtained.Moreover, since the 7- to 10-membered ring formed by the groups R³ or R⁶and the group A contain double bonds therein, the movements of thesubstituent groups R⁷, R⁸ and R^(a) are inhibited so that configurationof the ligands is firmly fixed. For this reason, it is considered thateven if the polymerization temperature is increased, it is possible toobtain a high-molecular weight polymer having an excellent stereoregularity.

EXAMPLES

The present invention is described in more detail below by way ofexamples, but these examples are not intended to limit the scope of thepresent invention. Incidentally, in the following examples, all thecatalyst preparation processes and polymerization processes wereconducted in a purified nitrogen atmosphere. In addition, solvents weredehydrated with MS-4A and then deaerated by bubbling with purifiednitrogen before they were used for these processes. Further, theactivity of each solid catalyst component per unit weight thereof isreferred to as “catalytic activity” and indicated by a unit of“g-polymer/g-solid catalyst component”, whereas the activity of eachcomplex component per unit weight thereof is referred to as “complexactivity” and indicated by a unit of “g-polymer/g-complex component”.

(1) Measurement of Melt Flow Rate (MFR)

Six grams of an acetone solution containing 0.6% by weight of a thermalstabilizer (BHT) was added to 6 g of the obtained polymer. After drying,the polymer was charged into a melt indexer (230° C.) and allowed tostand for 5 minutes under a load of 2.16 Kg. Thereafter, the polymer wasextruded to measure the amount of the extruded polymer. Based on thethus-measured amount of the extruded polymer, the amount per 10 minuteswas calculated and used as a value of MFR.

(2) Measurement of Molecular Weight Distribution

The molecular weight distribution of the obtained polymer was determinedfrom the Q-value (Mw/Mn) of weight-average molecular weight (Mw) tonumber-average molecular weight (Mn) thereof which were measured by gelpermeation chromatography (GPC). The measurement of the molecularweights was conducted at 135° C. by a GPC apparatus (150CV typemanufactured by Waters), using ortho-dichlorobenzene as a solvent.

(3) Measurement of Melting Point

Using a differential scanning calorimeter (DSC) manufactured by E. I. duPont, the melt flow rate of the obtained polymer was measured after thepolymer was heated two times from 20° C. to 200° C. at a heating rate of10° C./min.

(4) Measurement of Stereo Regularity

300 mg of the polymer sample was dissolved in a mixed solvent composedof 2.5 ml of ortho-dichlorobenzene and 0.5 ml of benzene-d₆. Theobtained solution was subjected to a nuclear magnetic resonance (NMR)analysis by using JEOL EX-270 Spectrometer. The NMR analysis wasconducted at a temperature of 130° C., an irradiation time of 0.744 secand a pulse delay of 2.256 sec, and cumulatively repeated 20,000 timesto determine a stereo regularity of the obtained polymer.

Example 1

(1) Chemical Treatment of Clay Minerals

Thirty grams of a 35% hydrochloric acid solution was diluted with 70 mlof desalted water. Next, 11.7 g of commercially availablemontmorillonite (“KUNIPIA F” produced by KUNIMINE INDUSTRIES CO., LTD.)was dispersed in the dilute solution. The resultant dispersion washeated up to a boiling point thereof while stirring and boiled for 2hours. Thereafter, the product was sufficiently washed with desaltedwater and, after pre-drying, dried at 200° C. for 2 hours under areduced pressure to obtain a component (B).

(2) Preparation of Solid Catalyst Component

3.0 g of the chemically treated montmorillonite obtained in the aboveitem (1) was charged into a 100 ml flask and dispersed in 20 ml oftoluene to obtain a slurry. Successively, 1.3 ml of triethylaluminum wasadded to the slurry at room temperature while stirring. After stirringthe slurry at room temperature for one hour, the supernatant was removedand the solid residue was washed with toluene to obtain a solid catalystcomponent.

(3) Synthesis of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} zirconium dichloride(component (A))

(a) Synthesis of Racemic and Meso Mixture

2.22 g of 2-methylazulene produced according to the method described inJapanese Patent Application Laid-Open (KOKAI) No. 62-207232, wasdissolved in 30 ml of hexane. 15.6 ml of a cyclohexane/diethyl ethersolution of phenyl lithium (1.0 equivalent) was gradually added to theabove-obtained hexane solution at 0° C. After stirring at roomtemperature for one hour, the obtained solution was cooled to −78° C.,and then mixed with 30 ml of tetrahydrofuran. The solution was mixedwith 0.95 ml of dimethyldichlorosilane and the temperature thereof wasraised to room temperature. The solution was further heated to 50° C.and stirred for 1.5 hours. After an aqueous ammonium chloride solutionwas added, the solution was separated into aqueous and organic phases.The organic phase was dried with magnesium sulfate and stirred under areduced pressure to remove the solvent. The thus-obtained crude productwas purified by column chromatography (hexane:dichloromethane=5:1) toobtain 1.48 g of dimethylbis{1,1′-(2-methyl-4-phenyl-1,4-dihydroazulenyl} silane.

768 mg of the thus-produced dimethylbis{1,1′-(2-methyl-4-phenyl-1,4-dihydroazulenyl} silane was dissolved in15 ml of diethyl ether. 1.98 ml of a hexane solution of n-butyl lithium(1.64 mol/liter) was dropped into the solution at −78° C., and thesolution was stirred for 12 hours while the temperature thereof wasgradually raised to room temperature. The solvent was removed under areduced pressure, thereby obtain a solid component. The obtained solidcomponent was washed with hexane, and then dried and solidified under areduced pressure. 20 ml of a mixed solvent composed of toluene anddiethyl ether (40:1) was added to the dried product, and further 325 mgof zirconium tetrachloride was added thereto at −60° C. The mixture wasstirred for 15 hours while the temperature thereof was gradually raisedto room temperature. The obtained solution was concentrated under areduced pressure and then mixed with hexane to obtain, as a precipitate,150 mg of a racemic and meso mixture of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} zirconium dichloride (amixture showing the below-mentioned spectrum data).

(b) Purification of Racemic Compound

887 mg of the above-produced racemic and meso mixture was dissolved in30 ml of dichloromethane and charged into a Pyrex vessel equipped with a100 W high-pressure mercury vapor lamp. While stirring, the solution wasirradiated (300 nm to 600 nm) for 30 minutes under atmospheric pressureto enhance a percentage of the racemic compound in the mixture, andstirred under a reduced pressure to remove the solvent. 7 ml of toluenewas added to the obtained yellow solid. After stirring, the mixture wasallowed to stand to precipitate the yellow solid, followed by removingthe supernatant. Similar washing procedures were repeated three timesusing 4 ml of toluene, 2 ml of toluene and 2 ml of hexane. Thethus-obtained solid product was dried and solidified under a reducedpressure to obtain 437 mg of a racemic compound of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} zirconium dichloride.

(c) Chemical Shift of ¹H-NMR of Racemic Compound

300 MHz, C₆D₆ (ppm) δ0.51 (s, 6H, Si(CH₃)₂), 1.92 (s, 6H, CH₃), 5.30 (brd, 2H), 5.75-5.95 (m, 6H), 6.13 (s, 2H), 6.68 (d, J=14 Hz, 2H),7.05-7.20 (m, 2H, arom), 7.56 (d, J=7 Hz, 4H)

(d) Chemical Shift of ¹H-NMR of Meso Compound

300 MHz, C₆D₆ (ppm) δ0.44 (s, 6H, SiCH₃), 0.59 (s, 6H, SiCH₃), 1.84 (s,6H, CH₃), 5.38 (br d, 2H), 5.75-6.00 (m, 6H), 6.13 (s, 2H), 6.78 (d,J=14 Hz, 2H), 7.00-7.20 (m, 2H, arom), 7.56 (d, J=7 Hz, 4H)

(4) Polymerization of Propylene

0.5 mmol (calculated as Al atom) of triethylaluminum (produced by TOSOHAKZO CORP.) and 100 mg of the solid catalyst component obtained in theabove item (2) were charged into a 2-liter stirring-type autoclave. Onthe other hand, 0.975 mg (1.5 μmol) of the above-prepared racemiccompound as a component (A) was diluted with 3 ml of toluene and chargedinto a catalyst feeder equipped with a safety rupture disc. Thereafter,1,500 ml of propylene was charged into the autoclave and the content ofthe autoclave was heated to 70° C. Successively, an argon gas having apressure of 80 kgf/cm²G was introduced into the catalyst feeder to breakthe safety rupture disc, so that the component (A) was supplied into theautoclave to initiate the polymerization of propylene.

After the polymerization was continued for 2 hours, unreacted propylenewas purged to obtain 166.5 g of polypropylene. As a result of themeasurements, it was confirmed that the catalyst activity was 1665 andthe complex activity was 17.1×10⁴. Further, it was confirmed that theobtained polypropylene had a melting point (Tm) of 150.1° C., a meltflow rate (MFR) of 2.5, a weight-average molecular weight (Mw) of3.1×10⁵ and a Q-value (Mw/Mn) of 2.8. The measurement of ¹³C-NMRspectrum showed that the [mmmm] was 98.9%, the 2,1-inversion was 0.9%and the 1,3-insertion was 0.08%. The results are shown in Tables 1 and2.

Reference Example 1 Polymerization of Propylene

4 mmol (calculated as Al atom) of methylalumoxane (“MMAO” produced byTOSOH AKZO CORP.) and 0.26 mg (0.4 μmol) of the racemic compoundobtained in Example 1 were charged into a 2-liter stirring-typeautoclave. Further, 1,500 ml of propylene was charged into the autoclaveand the content of the autoclave was heated to 70° C. to conduct thepolymerization of propylene for one hour, thereby obtaining 43.5 g ofpolypropylene. As a result of the measurements, it was confirmed thatthe complex activity was 16.7×10⁴ and the obtained polypropylene had amelting point (Tm) of 150.9° C., a melt flow rate (MFR) of 1.3, aweight-average molecular weight (MW) of 3.5×10⁵ and a Q-value (Mw/Mn) of2.7. Further, the measurement of ¹³C-NMR spectrum showed that the [mmmm]was 99.0%, the 2,1-inversion was 0.9% and the 1,3-insertion was 0.10%.The results are shown in Tables 1 and 2.

Example 2 Polymerization of Propylene

The same procedure as defined in Example 1(3) was conducted except thatthe polymerization temperature was changed to 80° C., to obtain 235 g ofpolypropylene. As a result of the measurements, it was confirmed thatthe catalyst activity was 2350 and the complex activity was 24.1×10⁴,and the obtained polypropylene had a melting point (Tm) of 148.8° C., amelt flow rate (MFR) of 8.5, a weight-average molecular weight (Mw) of2.1×10⁵ and a Q-value (Mw/Mn) of 2.7. Further, the measurement of¹³C-NMR spectrum showed that the [mmmm] was 98.8%, the 2,1-inversion was0.9% and the 1,3-insertion was 0.06%. The results are shown in Tables 1and 2.

Example 3

Polymerization of Propylene

500 ml of dried and deaerated toluene, 0.5 mmol (calculated as Al atom)of triethylaluminum (produced by TOSOH AKZO CORP.) and 100 mg of thesolid catalyst component obtained in the above Example 1(2) were chargedinto a 1.5-liter stirring-type autoclave whose interior was sufficientlydried and replaced with a propylene gas. While maintaining at 20° C.,the autoclave was charged with 4 μmol of the racemic compound obtainedin Example 1. Thereafter, the reaction system in the autoclave washeated to 70° C. to initiate the polymerization of propylene whileadjusting the propylene pressure in the autoclave to 5 kgf/cm²G. Afterthe polymerization was continued for one hour, unreacted propylene waspurged and obtained a slurry containing a polymer. The slurry wasfiltered and dried to recover 17 g of polypropylene. Further, thefiltrate was concentrated so that 0.05 g of polypropylene dissolved inthe filtrate was recovered. As a result of the measurements, it wasconfirmed that the catalyst activity was 170 and the complex activitywas 0.65×10⁴, and the obtained polypropylene had a melting point (Tm) of150.9° C., a melt flow rate (MFR) of 3.5, a weight-average molecularweight (Mw) of 3.0×10⁵ and a Q-value (Mw/Mn) of 2.8. The measurement of¹³C-NMR spectrum showed that the [mmmm] was 99.0%, the 2,1-inversion was0.7% and the 1,3-insertion was 0.10%. The results are shown in Tables 1and 2.

Example 4

(1) Chemical Treatment and Granulation of Clay Minerals

3 Kg of commercially available montmorillonite was pulverized by avibrating ball mill and dispersed in 16 liters of 3% hydrochloric acidsolution. The dispersion was heated at 90° C. for 3 hours while stirringto obtain an aqueous slurry of chemically treated montmorillonite.Successively, after the solid content of the aqueous slurry was adjustedto 15%, the slurry was sprayed by means of a spray drier to conductgranulation of the solid component, followed by washing with desaltedwater. The thus-obtained particles had a spherical shape.

Next, 10.0 g of the chemically treated montmorillonite obtained in theabove was charged into a 200 ml flask and subjected to heating anddesiccation treatment at 200° C. for 2 hours under a reduced pressure.It was confirmed that the weight of the montmorillonite was reduced by1.3 g as a result of the heating and desiccation treatment.

(2) Preparation of Solid Catalyst Component

3.0 g of the chemically treated montmorillonite obtained in the above(1) was charged into a 100 ml flask and dispersed in 20 ml of toluene toobtain a slurry. Successively, 1.3 ml of triethylaluminum was added tothe slurry at room temperature while stirring. After both the componentswere contacted with each other at room temperature for one hour, thesupernatant was removed and the solid residue was washed with toluene toobtain a solid catalyst component.

(3) Polymerization of Propylene

0.5 mmol (calculated as Al atom) of triethylaluminum (produced by TOSOHAKZO CORP.), 100.0 mg of the solid catalyst component obtained in theabove (2) and 750 g of liquid propylene were charged into a 2-literstirring-type autoclave. Thereafter, the content of the autoclave washeated to 70° C. and then supplied with 5.0 ml of a toluene solutioncontaining dimethylsilylene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl}zirconium dichloride (2.0 μmol/ml) as a complex component. Thepolymerization of propylene was continued at 70° C. for 2 hours whilestirring. After completion of the polymerization, unreacted propylenewas purged to obtain 180 g of polypropylene. As a result of themeasurements, it was confirmed that the catalyst activity was 1800 andthe complex activity was 2.7×10⁴, and the obtained polypropylene had amelting point (Tm) of 148.4° C., a melt flow rate (MFR) of 11.1, aweight-average molecular weight (Mw) of 1.9×10⁵ and a Q-value (Mw/Mn) of2.7. Further, the measurement of ¹³C-NMR spectrum showed that the [mmmm]was 98.8%, the 2,1-inversion was 0.9% and the 1,3-insertion was 0.10%.The results are shown in Tables 1 and 2.

Example 5

Copolymerization of Propylene and Ethylene

0.5 mmol (calculated as Al atom) or triethylaluminum, 100.0 mg of thesolid catalyst component obtained in Example 1 and 750 g of liquidpropylene were charged into a 2-liter stirring-type autoclave. After thecontent of the autoclave was heated to 70° C., 3.0 ml of a toluenesolution containing dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} zirconium dichloride (2.0μmol/ml) as a complex component was supplied into the autoclave togetherwith pressurized ethylene. The supply of ethylene was continued suchthat the mole percentage of (ethylene) to (propylene+ethylene) in a gascomposition within the autoclave was 3.5 mol %. Under this condition,the polymerization of propylene was continued at 70° C. for 2 hourswhile stirring. After completion of the polymerization, unreactedpropylene and unreacted ethylene were purged to obtain 230 g ofpolypropylene/ethylene copolymer. As a result of the measurements, itwas confirmed that the catalyst activity was 3830, the complex activitywas 5.9×10⁴, and the thus-obtained polypropylene/ethylene copolymer hadan ethylene content of 0.8 mol %, a melting point (Tm) of 141.7° C., amelt flow rate (MFR) of 9.7, a weight-average molecular weight (Mw) of2.1×10⁵ and a Q-value (Mw/Mn) of 2.6. Further, the measurement of¹³C-NMR spectrum showed that the [mmmm] was 98.8%, the 2,1-inversion was0.8% and the 1,3-insertion was 0.08%. The results are shown in Tables 1and 2.

Comparative Example 1

(1) Synthesis of dimethylsilylene bis{1,1′-(2-methyl-4,5-benzoindenyl}zirconium dichloride

Dimethylsilylene bis{1,1′-(2-methyl-4,5-benzoindenyl} zirconiumdichloride was synthesized according to the method described in Example7 of Japanese Patent Application Laid-open (KOKAI) No. 8-208733.

(2) Polymerization of Propylene

The same procedure as defined in Example 1 was conducted except that theafore-mentioned compound (in item (1)) was used as the component (A) andthe polymerization time was one hour, to obtain 160 g of polypropylene.As a result of the measurements, it was confirmed that the catalystactivity was 1600, the complex activity was 5.8×10⁴, and the obtainedpolypropylene had a melting point (Tm) of 132.0° C., a melt flow rate(MFR) of 200, a weight-average molecular weight (Mw) of 1.1×10⁵ and aQ-value (Mw/Mn) of 2.2. Further, the measurement of ¹³C-NMR spectrumshowed that the [mmmm] was 95.1%, the 2,1-inversion was 0.8% and the1,3-insertion was not detected. The results are shown in Tables 1 and 2.

Comparative Example 2

Polymerization of Propylene

The same procedure as defined in Reference Example 1 was conductedexcept that the afore-mentioned compound synthesized in ComparativeExample 1 was used as the component (A) and the polymerizationtemperature was adjusted to 70° C., to obtain 155.2 g of polypropylene.As a result of the measurements, it was confirmed that the complexactivity was 67.5×10⁴, and the obtained polypropylene had a meltingpoint (Tm) of 151.5° C., a melt flow rate (MFR) of 2.0, a weight-averagemolecular weight (Mw) of 3.8×10⁵ and a Q-value (Mw/Mn) of 2.1. Further,the measurement of ¹³C-NMR spectrum showed that the [mmmm] was 95.5%,the 2,1-inversion was 0.4% and the 1,3-insertion was not detected. Theresults are shown in Tables 1 and 2.

TABLE 1 Evaluation (catalyst Catalyst performance) Com- Com- Complexponent ponent Conditions of Catalytic activity (A) (C) polymerizationactivity (× 10⁴) Ex. 1 (1)* Triethyl 70° C./bulk/2 Hr 1665 17.1 aluminumRef. (1) MMAO 70° C./bulk/1 Hr — 16.7 Ex. 1 Ex. 2 (1) Triethyl 80°C./bulk/2 Hr 2350 24.1 aluminum Ex. 3 (1) Triethyl 70° C.,  170 0.65aluminum 5 kgf/cm²G/ slurry/ 1 Hr Ex. 4 (1) Triethyl 70° C./bulk/2 Hr1800 2.7 aluminum Ex. 5 (1) Triethyl 70° C./bulk + 3830 5.9 aluminumethylene/2 Hr Comp. (2)** Triethyl 70° C./bulk/1 Hr 1600 5.8 Ex. 1aluminum Comp. (2) MMAO 70° C./bulk/1 Hr — 67.5 Ex. 2 Note: (1)*:dimethylsilylene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} zirconiumdichloride; (2)**: dimethylsilylene bis{1,1′-(2-methyl-4,5-benzoindenyl}zirconium dichloride

TABLE 2 Properties of poylmer Melting MFR Mw Q point (° C.) (g/10 min)(× 10⁵) (Mw/Mn) Example 1 150.1 2.5 3.1 2.8 Reference 150.9 1.3 3.5 2.7Example 1 Example 2 148.8 8.5 2.1 2.7 Example 3 150.9 3.5 3.0 2.8Example 4 148.4 11.1 1.9 2.7 Example 5 141.7 9.7 2.1 2.6 Comparative132.0 200 1.1 2.2 Example 1 Comparative 151.5 2.0 3.8 2.1 Example 2Properties of polymer [mmmm] (%) 2,1-(mol %) 1,3-(mol %) Example 1 98.90.9 0.08 Reference 99.0 0.9 0.10 Example 1 Example 2 98.8 0.9 0.06Example 3 99.0 0.7 0.10 Example 4 98.8 0.9 0.10 Example 5 98.8 0.8 0.08Comparative 95.1 0.8 not detected Example 1 Comparative 95.5 0.4 notdetected Example 2

Example 6

(1) Synthesis of dimethylsilylenebis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl} zirconium dichloride ascomponent (A)

(a) Synthesis of Tosyltropolone

25.58 g (210 mmol) of tropolone was dissolved in 30 ml of pyridine. 60ml of a pyridine solution containing 40.77 g (214 mmol) of tosylchloride was added to the tropolone-containing solution at roomtemperature. After stirring overnight at room temperature, the resultantreaction solution was supplied with water to deposit a crystallizedproduct. The crystallized product was separated by filtration and driedat 50° C. under a reduced pressure to obtain 57.61 g of tosyltropolone(yield: 99.5%).

(b) Synthesis of 3-propionylcycloheptafuran-2-one

8.07 g (29.2 mmol) of tosyl tropolone and 6.2 ml (43.8 mmol) of ethylpropionylacetate were suspended in 30 ml of ethanol. A solutioncontaining sodium ethoxide prepared from 60 ml of ethanol and 806 mg(35.1 mmol) of sodium was added to the suspension at 0° C. The mixturewas stirred overnight at room temperature and then heated at 50° C. for45 minutes. The resultant reaction solution was concentrated up to twotimes an initial concentration thereof. The concentrated solution wassupplied with water to obtain a crystallized product. The crystallizedproduct was separated from the reaction solution by filtration. Further,the filtrate was concentrated to crystallize the reaction productremaining therein. The crystallized product obtained from the filtratewas also separated from the solution by filtration. The productsthus-obtained from the reaction solution and the filtrate were mixedtogether and dried under a reduced pressure to obtain 3.62 g of3-propionylcycloheptafuran-2-one (yield: 61%).

(c) Synthesis of 1-cyano-2-ethylazulene-3-carboxylic acid

3.62 g (17.9 mmol) of 3-propionylcycloheptafuran-2-one and 3.8 ml (35.8mmol) of ethyl cyanoacetate were dissolved in 50 ml of ethanol. Thesolution was mixed with a solution of sodium ethoxide prepared from 80ml of ethanol and 1.65 g (71.7 mmol) of sodium, at 0° C. After the mixedsolution was stirred overnight at room temperature, the obtainedreaction solution was concentrated up to two times an initialconcentration thereof. The concentrated solution was diluted with 200 mlof water and extracted with dichloromethane. Thereafter, an aqueousphase of the extract was mixed with dilute hydrochloric acid to acidifythe aqueous phase, thereby obtaining a crystallized product. Afterfiltration, the crystallized product was dried under a reduced pressureto obtain 3.73 g of 1-cyano-2-ethylazulene-3-carboxylic acid (yield:93%).

(d) Synthesis of 2-ethylazulene

3.7 g (16.4 mmol) of the above-obtained1-cyano-2-ethylazulene-3-carboxylic acid was separated into two parts,i.e., about 1 g and a remaining part. 30 ml of 75% sulfuric acid wasadded to the first part, i.e., about 1 g of1-cyano-2-ethylazulene-3-carboxylic acid and heated to 90° C., andthereafter gradually supplied with the remaining part of1-cyano-2-ethylazulene-3-carboxylic acid. The mixture was heated at 90°C. for 2 hours and further at 120° C. for 2 hours. The obtained reactionsolution was added to an aqueous solution containing 35 g of sodiumhydroxide and extracted with a mixed solution of hexane and ethylacetate. An organic phase of the extract was removed under a reducedpressure. The resultant crude product was purified by silica gel columnchromatography, to obtain 1.71 g of 2-ethyl azulene (yield: 67%).

(e) Synthesis of bis(1,1′-(2-ethyl-4-phenyl-1,4-dihydroazulenyl}dimethyl silane

A diethyl ether/cyclohexane solution containing 10.9 mmol (0.1 M) ofphenyl lithium was added to 20 ml of a hexane solution containing 1.7 g(10.9 mmol) of 2-ethylazulene at 0° C. After stirring at roomtemperature for 1.5 hours, the solution was mixed with 20 ml oftetrahydrofuran at 0° C. Further, 0.66 ml (5.45 mmol) ofdichlorodimethylsilane was added to the solution at −78° C., followed bystirring at room temperature for one hour and then at 50° C. for 3hours. After the mixed solution was allowed to stand at room temperatureovernight, an aqueous solution of ammonium chloride was added theobtained reaction solution. The solution was separated into aqueous andorganic phases. The organic phase was dried with magnesium sulfate, andthe solvent was removed under a reduced pressure. The obtained crudeproduct was purified by a column chromatography using a mixed solventcomposed of hexane and dichloromethane (10:1 to 5:1) as an eluentsolvent to obtain 1.07 g of bis{1,1′-(2-ethyl-4-phenyl dihydroazulenyl}dimethyl silane (yield: 37%).

(f) Synthesis of dimethylsilylenebis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl} zirconium dichloride

A hexane solution containing 6.62 mmol of n-butyl lithium was added to15 ml of a diethyl ether solution containing 3.32 mmol of theabove-produced bis{1,1′-(2-ethyl-4-phenyl-1,4-dihydroazulenyl}dimethylsilane at −78° C. After the solution was stirred at roomtemperature overnight, the solvent was removed under reduced pressure.10 ml of toluene and 0.25 ml of diethyl ether were added to the productto form a solution, and 775 mg (3.32 mmol) of zirconium tetrachloridewas added to the solution at −70° C. The temperature of obtainedreaction solution was gradually raised to room temperature and stirredat room temperature for 3 hours. Successively, the reaction solution wasfiltered through celite, and the obtained solid component was washedwith 6 ml of toluene and 6 ml of hexane. The thus-obtained solidcomponent was dissolved in 30 ml of dichloromethane, and the solvent wasremoved under a reduced pressure. The resultant concentrated solutionwas supplied with 10 ml of hexane to form a precipitate. The precipitatewas separated from the solution, and then dried and solidified under areduced pressure to obtain 450 mg of a racemic and meso mixture ofdimethylsilylene bis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl} zirconiumdichloride (yield: 20%).

(a) Purification of Racemic Compound

400 mg of the above-produced racemic and meso mixture was dissolved in15 ml of dichloromethane and charged into a Pyrex vessel equipped with a100 W high-pressure mercury vapor lamp. While stirring, the solution wasirradiated with light under normal pressure for 10 minutes to enhancethe percentage of the racemic compound therein. Thereafter,dichloromethane was removed under a reduced pressure. The obtainedyellow solid was mixed with 5 ml of toluene to form a solution, followedby stirring the solution. After the solution was filtered, the obtainedsolid component was washed with 6 ml of hexane to obtain 173 mg of theracemic compound of dimethylsilylenebis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl} zirconium dichloride.

The chemical shifts of ¹H-NMR of the above-obtained racemic compound areas follows.

300 MHz, CDCl₃ (ppm) 1.00 (s, 6H, SiMe₂), 1.05 (t, ³J=8 Hz, 6H, CH₃CH₂),2.42 (sext, ³J=8 Hz, ²J=15 Hz, 2H, CH₃CHH′), 2.60 (sext, ³J=8 Hz, ²J=15Hz, 2H, CH₃CHH′), 4.94 (br s, 2H, 4-H), 5.83-5.95 (m, 4H), 5.99 (s, 2H),6.08-6.12 (m, 2H), 6.75 (d, 2H, 8-H), 7.2-7.4 (m, 10H, arom).

(2) Polymerization of Propylene

0.45 mmol of triethylaluminum, a slurry of chemically treated clayminerals described hereinafter in Example 11(2) and 700 ml of liquidpropylene were charged into a 1-liter stirring-type autoclave at roomtemperature in the presence of a nitrogen stream. Further, 1.5 μmol ofthe racemic compound of dimethylsilylenebis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl} zirconium dichlorideproduced in the above item (1) was dissolved in toluene, and thesolution was charged into the autoclave together with a high pressureargon gas breaking through the safety rupture disk. The content of theautoclave was heated to 80° C. and the polymerization of propylene wasconducted for one hour. Thereafter, unreacted propylene was purged toterminate the polymerization of propylene, thereby obtaining 180 g ofpolypropylene. As a result of the measurements, it was confirmed thatthe catalyst activity was 3600 and the complex activity was 17.6×10⁴,and the obtained polypropylene had a melting point (Tm) of 149.2° C., amelt flow rate (MFR) of 11, a weight-average molecular weight (Mw) of20×10⁵ and a Q-value (Mw/Mn) of 2.5.

Reference Example 2

Polymerization of Propylene

4 mmol (calculated as Al atom) of methylalumoxane (“MMAO” produced byTOSOH AKZO CORP.) and a toluene solution containing 0.27 mg of a racemiccompound of dimethylsilylene bis{1,1′-(2-ethyl-4-phenyl-4-hydroazulenyl}zirconium dichloride were charged into a 2-liter stirring-typeautoclave. Further, 1,500 ml of propylene was introduced into theautoclave. The content of the autoclave was heated to 70° C., and thepolymerization of propylene was conducted for one hour to obtain 239 gof polypropylene. As a result of the measurements, it was confirmed thatthe complex activity was 87.2×10⁴, and the obtained polypropylene had amelting point (Tm) of 155.2° C., a melt flow rate (MFR) of 0.6, aweight-average molecular weight (Mw) of 4.7×10⁵ and a Q-value (Mw/Mn) of3.1.

Example 7

(1) Chemical Treatment of Clay Minerals

10 g of lithium hectorite (Li-HT produced by TOPY KOGYO CO., LTD.) wasweighed and charged into a 300 ml round bottom flask. 100 ml of desaltedwater was introduced into the flask to form a slurry. The slurry wascharged into a mechanical stirrer. While stirring the slurry, 8.9 ml ofTiCl₄ (EXTRA-HIGH GRADE produced by KISHIDA CHEMICAL CO., LTD.) wasgradually dropped thereinto at room temperature. The slurry was furtherstirred for 3 hours, and then filtered to remove a solid componenttherefrom. The obtained solid component was washed with water until thepH of filtrate thereof became 5.0. After drying at 100° C. for 3 hours,the obtained filter cake was pulverized in a porcelain mortar and passedthrough a sieve to separate particles having a particle size of not morethan 105 μm from the remainder. The thus-obtained particles were driedat 200° C. for 2 hours under a reduced pressure to obtain the component(B).

(2) Preparation of Solid Catalyst Component

1.2 g of the TiCl₄-treated lithium hectorite obtained in the above item(1) was weighed and charged into a 100 ml flask in a nitrogenatmosphere. 12 ml of toluene was added into the flask to form a slurry.Separately, a toluene solution of triethylaluminum (0.9 mol/liter) wasprepared. While the slurry containing TiCl₄-treated lithium hectoritewas stirred, 6.4 ml of the separately prepared toluene solution oftriethylaluminum was introduced into the slurry at room temperature. Theslurry was stirred at room temperature for one hour, and then washedwith toluene until the washing efficiency reached 1/100. As a result ofthe measurement, it was confirmed that the concentration of the slurrywas 52.6 mg/ml.

(3) Polymerization of Propylene

0.45 mmol of triisobutylaluminum, 1.9 ml of the catalyst slurry obtainedin the above (2) and 1,500 ml of liquid propylene were charged into a2-liter stirring-type autoclave at room temperature in the presence of anitrogen stream. Separately, 2.0 mg (3.0 μmol) of a racemic compound ofdimethylsilylene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} zirconiumdichloride was dissolved in 1.6 ml of toluene to form a solution. Thesolution was introduced into the autoclave together with a high pressureargon gas breaking through the safety rupture disk. The content of theautoclave was heated to 80° C. and the polymerization of propylene wasconducted at that temperature for one hour. Thereafter, unreactedpropylene was purged to terminate the polymerization of propylene,thereby obtaining 110 g of polypropylene. As a result of themeasurements, it was confirmed that the catalyst activity was 1100, thecomplex activity was 5.5×10⁴, and the obtained polypropylene had amelting point (Tm) of 147.0° C., a melt flow rate (MFR) of 24.2, aweight-average molecular weight (Mw) of 1.7×10⁵ and a Q-value (Mw/Mn) of2.9.

Example 8

(1) Chemical Treatment of Clay Minerals

10 g of lithium hectorite (Li-HT produced by TOPY KOGYO Co., LTD.) wasweighed and charged into a 300 ml round bottom flask. 100 ml of desaltedwater was introduced into the flask to form a slurry. The slurry wascharged into a mechanical stirrer. While stirring the slurry, 25 ml ofan aqueous solution containing 19.3 mg of AlCl₃ (EXTRA-HIGH GRADEproduced by Wako Pure Chemical Industries, LTD.) was gradually droppedthereinto at room temperature. The slurry was further stirred for 3hours, and then filtered to remove a solid component therefrom. Theobtained solid component was washed with water until the pH of filtratethereof became 5.0. After drying at 100° C. for 3 hours, the obtainedfilter cake was pulverized in a porcelain mortar and passed through asieve to separate particles having a particle size of not more than 105μm from the remainder. The thus-obtained particles were dried at 200° C.for 2 hours under a reduced pressure to obtain the component (B).

(2) Preparation of Solid Catalyst Component

1.1 g of the AlC1₃-treated lithium hectorite obtained in the above item(1) was weighed and charged into a 100 ml flask in a nitrogenatmosphere. 10 ml of toluene was added into the flask to form a slurry.While stirring the slurry containing the AlCl₃-treated lithiumhectorite, 5.5 ml of a toluene solution of triethylaluminum (0.91mol/liter) was introduced thereinto at room temperature. After stirringat room temperature for one hour, the slurry was washed with tolueneuntil the washing efficiency reached 1/100. As a result of themeasurement, it was confirmed that the concentration of the slurry was35.7 mg/ml.

(3) Polymerization of Propylene

0.45 mmol of triisobutylaluminum, 2.8 ml of the solid catalyst componentslurry obtained in the above item (2) and 1,500 ml of liquid propylenewere charged into a 2-liter stirring-type autoclave at room temperaturein the presence of a nitrogen stream. Separately, 2.0 mg (3.0 μmol) of aracemic compound of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} zirconium dichloride wasdissolved in 1.6 ml of toluene to prepare a solution. The solution wasintroduced into the autoclave together with a high pressure argon gasbreaking through the safety rupture disk. The content of the autoclavewas heated to 80° C., and the polymerization of propylene was conductedat that temperature for one hour. Thereafter, unreacted propylene waspurged to terminate the polymerization of propylene, thereby obtaining68 g of polypropylene. As a result of the measurements, it was confirmedthat the catalyst activity was 660, the complex activity was 3.4×10⁴,and the obtained polypropylene had a melting point (Tm) of 147.3° C. anda melt flow rate (MFR) of 24.2.

Example 9

(1) Synthesis of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} hafnium dichloride

(a) Synthesis of Racemic and Meso Mixture

3.22 g of 2-methylazulene was dissolved in 30 ml of hexane. 21 ml of acyclohexane/diethyl ether solution of phenyl lithium (1.0 equivalent)was gradually added to the hexane solution at 0° C. After stirring atroom temperature for 1.5 hours, the resultant solution was cooled to−78° C. and then mixed with 30 ml of tetrahydrofuran. The solution wasfurther supplied with 45 μmol of 1-methylimidazole and 1.37 ml ofdimethyldichlorosilane and the temperature thereof was raised to roomtemperature. The solution was stirred for one hour. After an aqueousammonium chloride solution was added, the solution was separated intoaqueous and organic phases. The organic phase separated was dried withmagnesium sulfate and stirred under a reduced pressure to remove thesolvent, thereby obtaining 5.84 g of a crude product ofbis{1,1′-(2-methyl-4-phenyl-1,4-dihydroazulenyl} dimethylsilane.

The thus-obtained crude product ofbis{1,1′-(2-methyl-4-phenyl-1,4-dihydroazulenyl} dimethylsilane wasdissolved in 30 ml of diethyl ether. 14.2 ml of a hexane solution ofn-butyl lithium (1.64 mol/liter) was dropped into the solution at −78°C., and the temperature of the solution was gradually raised to roomtemperature and stirred at room temperature for 12 hours. The solutionwas stirred under a reduced pressure to remove the solvent. Thereafter,80 ml of a mixture of toluene and dimethyl ether (40:1) was added to thesolution. Further, the solution was mixed with 3.3 g of hafniumtetrachloride at −60° C. and temperature thereof was gradually raised toroom temperature, followed by stirring at room temperature for 4 hours.The obtained solution was concentrated under a reduced pressure toobtain a solid product. The obtained solid product was washed withtoluene and extracted with dichloromethane to obtain 1.74 g of a racemicand meso mixture of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} hafnium dichloride.

(b) Purification of Racemic Compound

1.74 g of the racemic and meso mixture prepared by repeatedly conductingthe above-mentioned reaction was dissolved in 30 ml of dichloromethaneand charged into a Pyrex vessel equipped with a 100 W high-pressuremercury vapor lamp. While stirring, the solution was irradiated withlight for 40 minutes under normal pressure to enhance a percentage ofthe racemic compound therein, and stirred under a reduced pressure toremove dichloromethane. 10 ml of toluene was added to the obtainedyellow solid. After stirring, the mixture was filtered to separate asolid component therefrom. The thus-obtained solid component was washedwith 8 ml of toluene and 4 ml of hexane to obtain 917 mg of a racemiccompound of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} hafnium dichloride.

(2) Polymerization of Propylene

The same procedure as defined in Example 13(2) described hereinafter wasconducted except that 1.12 mg of the racemic compound obtained in theabove item (1) was used as the component (A) and the polymerization timewas changed to 35 minutes, to obtain 163 g of polypropylene. As a resultof the measurements, it was confirmed that the catalyst activity was3260 and the complex activity was 25.0×10⁴. Further, it was confirmedthat the obtained polypropylene had a melting point (Tm) of 152.7° C., amelt flow rate (MFR) of 0.8, a weight-average molecular weight (Mw) of4.1×10⁵ and a Q-value (Mw/Mn) of 2.6.

Reference Example 3

4 mmol (calculated as Al atom) of methylalumoxane (“MMAO” produced byTOSOH AKZO CORP.) and 0.298 mg of the racemic compound obtained in theabove item (1) of Example 9 were charged into a 2-liter stirring-typeautoclave. Further, 1,500 ml of propylene was introduced into theautoclave. The content of the autoclave was heated to 70° C., and thepolymerization of propylene was conducted at that temperature for onehour to obtain 32 g of polypropylene. As a result of the measurements,it was confirmed that the complex activity was 10.7×10⁴, and theobtained polypropylene had a melting point (Tm) of 154.4° C., a meltflow rate (MFR) of 0.08, a weight-average molecular weight (Mw) of8.4×10⁵ and a Q-value (Mw/Mn) of 3.8.

Example 10

(1) Chemical Treatment of Clay Minerals

22.20 g of commercially available montmorillonite (“KUNIPIA F” producedby KUNIMINE INDUSTRIES CO., LTD.) was dispersed in a solution preparedby dissolving 15.96 g of MgSO₄ in 134 ml of desalted water. Theresultant dispersion was heated at 86° C. for one hour while stirring,thereby obtaining a wet cake. Next, the thus-obtained wet cake wasdispersed in a solution prepared by dissolving 23.38 g of sulfuric acidand 29.16 g of MgSO₄ in 69.24 ml of desalted water, and then treatedunder reflux for 2 hours. Thereafter, the dispersion was filtered toseparate a cake therefrom. The obtained cake was washed with water untilthe pH of filtrate therefrom reached 6. The resultant product was driedat 100° C. for 3 hours, pulverized in a porcelain mortar and passedthrough a sieve to separate particles having not more than 105 μm. Theparticles were dried at 200° C. for 2 hours under a reduced pressure,thereby obtaining the component (B).

(2) Production of Solid Catalyst Component and Pre-polymerization ofPropylene

0.8796 g of the component (B) obtained in the above (1) was charged intoa 100 ml flask in a nitrogen atmosphere. In addition, 3.5 ml of atoluene solution containing triethylaluminum in an amount of 0.50mmol/ml was charged into the flask, and then mixture in the flask wasstirred at room temperature for 45 minutes. Next, the mixture wasfiltered to separate a solid component therefrom. The thus-separatedsolid component was washed with toluene until the washing efficiencyreached 1/100. Thereafter, the solid component was mixed with 15 ml oftoluene to prepare a toluene slurry.

Separately, 0.6 ml of a toluene solution of triisobutylaluminum (0.50mmol/ml) and 19.1 ml of a toluene solution of racemic dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)} hafnium dichloride (1.5μmol/ml) obtained in Example 9(1) were charged into a 100 ml flask, andstirred at room temperature to obtain a solution. The thus-obtainedsolution was mixed with the above-prepared toluene slurry to form aslurry containing a solid catalyst component.

A 2-liter stirring-type autoclave was charged with 40 ml of toluene andthen with 36 ml of the above-prepared slurry containing the solidcatalyst component, at room temperature in the presence of a nitrogenstream. While maintaining the temperature of the autoclave at 24° C.,104 ml of propylene was introduced into the autoclave and subjected topre-polymerization for 3 minutes to obtain a pre-polymerization catalystslurry. The amount of the polymer obtained by the pre-polymerization was2.98 g per one gram of the solid catalyst component. The concentrationof the solid catalyst component in the obtained pre-polymerizationcatalyst slurry was 12.5 mg/ml.

(3) Block Copolymerization of Propylene

0.40 mmol of triisobutylaluminum, the pre-polymerization catalyst slurryobtained in the above (2) which contained 50.0 mg of the solid catalystcomponent, 200 ml of hydrogen and 1,500 ml of liquid propylene wereintroduced into a 2-liter stirring-type autoclave. Thereafter, thecontent of the autoclave was heated to 75° C. to conduct thepolymerization of propylene for 45 minutes. Thereafter, unreactedpropylene was purged to terminate the polymerization of propylene,thereby obtaining 289 g or polypropylene. As a result of themeasurements, it was confirmed that the catalyst activity was 5780, thecomplex activity was 2.4×10⁵, and the obtained polypropylene had amelting point (Tm) of 151.8° C. and a melt flow rate (MFR) of 14.2.

After 17 g of the obtained polypropylene was removed from the autoclave,while maintaining the content of the autoclave at 60° C., the autoclavewas supplied with propylene and then ethylene until propylene andethylene pressures within the autoclave reached 10 kgf/cm²G and 20kgf/cm²G, respectively. The thus-supplied propylene and ethylene werepolymerized with each other for 80 minutes while introducing a mixed gasof ethylene and propylene having a propylene partial pressure of 49.97%to maintain an internal pressure of the autoclave at 20 kgf/cm²G.Thereafter, the mixed gas of ethylene and propylene was purged toterminate the polymerization, thereby obtaining 46 g of aethylene/propylene rubber component. As a result of the measurements, itwas confirmed that the catalytic activity was 978, the complex activitywas 4.0×10⁴, and the content of rubber component in the obtained blockcopolymer was 14.5% by weight and a melt flow rate (MFR) of 7.0.

Example 11

(1) Synthesis of dimethylgermylene{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} zirconium dichloride

1.5 g of 2-methylazulene was dissolved in 38 ml of n-hexane. 9.8 ml of acyclohexane/diethyl ether solution of phenyl lithium (1.08 M) wasgradually dropped into the n-hexane solution at a temperature of 3° C.to 5° C. After stirring at room temperature for one hour, the resultantsolution was cooled to 0° C., and then 38 ml of tetrahydrofuran wasadded. Further, 0.02 ml of 1-methylimidazole and 0.61 ml ofdimethylgermanium dichloride were dropped into the solution. Afterstirring at 0° C. for 20 minutes, the temperature of the reactionsolution was raised to room temperature, followed by stirring at roomtemperature for 3.5 hours. The reaction solution was mixed with asaturated aqueous solution of ammonium chloride and extracted withn-hexane. The extract was separated into aqueous and organic phases. Theorganic phase was washed with a saturated brine, and dried withmagnesium sulfate. The dried product was stirred under a reducedpressure to remove the solvent remaining therein. 2.9 g of thethus-obtained concentrated residue was purified by a columnchromatography, thereby obtaining 2.4 g of an amorphous solid product.

Next, 2.4 g of the thus-obtained amorphous solid product was dissolvedin 30 ml of diethyl ether. 5.6 ml of an n-hexane solution of n-butyllithium (1.59 M) was dropped into the diethyl ether solution at −78° C.After stirring at that temperature for 10 minutes, the temperature ofthe solution was gradually raised to room temperature. After furtherstirring at room temperature for 2 hours, the solution was allowed tostand overnight. The reaction solution was stirred under a reducedpressure to remove the solvent, and then mixed with 20 ml of toluene and0.5 ml of diethyl ether. After cooling to −78° C., the reaction solutionwas mixed with 1.0 g of zirconium tetrachloride, the reactiontemperature was gradually increased to room temperature, followed bystirring at room temperature for 5 hours in total. The obtained reactionsolution was filtered through celite to separate a solid componenttherefrom. The thus-obtained solid component was washed with 5 ml oftoluene two times and then extracted with dichloromethane. The extractwas stirred under a reduced pressure to remove the solvent, therebyobtaining 0.93 g of a racemic and meso mixture (ratio of racemic to mesoabout 6:4) of dimethylgermylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} zirconium dichloride(yield: 30%).

The chemical shifts of ¹H-NMR of the above-obtained racemic and mesomixture are as follows.

300 MHz; CDCl₃ (ppm) 1.14 (s, meso SiMe), 1.18 (s, meso SiMe), 1.20 (s,meso SiMe), 2.16 (s, 2-Me), 4.98-5.00 (m, —CH═), 5.06-5.08 (m, —CH═),5.83-5.94 (m, —CH═), 6.06-6.3 (m, —CH═), 6.67 (s, —CH═), 6.71 (s, —CH═),7.2-7.5 (m, aromatic ring)

(2) Chemical Treatment of Clay Minerals and Preparation of SolidCatalyst Component

10 g of montmorillonite (“KUNIPIA F” produced by KUNIMINE INDUSTRIESCO., LTD.) was dispersed in dilute sulfuric acid composed of 10 g ofsulfuric acid and 90 ml of desalted water. The resultant dispersion washeated up to a boiling point thereof, followed by stirring at thattemperature for 6 hours. Thereafter, the montmorillonite recovered wassufficiently washed with desalted water and, after pre-drying, dried at200° C. for 2 hours to obtain a chemically treated clay minerals. 200 mgof the chemically treated montmorillonite was added to 0.8 ml of atoluene solution of triethylaluminum (0.5 mol/liter). The mixture wasstirred at room temperature for one hour, and then washed with tolueneto obtain a montmorillonite/toluene slurry containing montmorillonite inan amount of 20 mg/ml.

(3) Polymerization of Propylene

0.5 mmol (calculated as Al atom) of triisobutylaluminum (produced byTOSOH AKZO CORP.) was charged into a 2-liter stirring-type autoclave.Separately, 2.1 mg of the above-prepared racemic and meso mixture ofdimethylgermylene {1,1′-(2-methyl-4-phenyl-4-hydroazulenyl} zirconiumdichloride obtained in the above (1) was diluted with 1.1 ml of toluene.The diluted racemic and meso mixture was charged into a catalyst feederequipped with a safety rupture disc. Further, 100 mg of thetriethylaluminum-treated montmorillonite obtained in the above (2) and0.3 mmol (calculated as Al atom) of triisobutylaluminum were chargedinto the autoclave. Thereafter, 1,500 ml of propylene was introducedinto the autoclave and the safety rupture disc of the catalyst feederwas broken at room temperature. After the content of the autoclave washeated to 80° C., and the polymerization of propylene was conducted atthat temperature for one hour, thereby obtaining 69 g of polypropylene.As a result of the measurements, it was confirmed that the catalystactivity was 690 and the complex activity was 3.3×10⁵. Further, it wasconfirmed that the polypropylene insoluble in boiled heptane had amelting point (Tm) of 147.9° C., a melt flow rate (MFR) of 7.3, aweight-average molecular weight (Mw) of 2.4×10⁵ and a Q-value (Mw/Mn) of2.4.

Example 12

(1) Synthesis of dimethylsilylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride

(a) Synthesis of Racemic and Meso Mixture

11.7 ml of a pentane solution containing 19.2 mmol of t-butyl lithium(1.64 M) was dropped into a solution prepared by dissolving 1.84 g (9.6mmol) of 1-bromo-4-chlorobenzene in a mixed solvent composed of 10 ml ofn-hexane and 10 ml of diethyl ether, at −78° C. The resultant solutionwas stirred at −5° C. for 1.5 hours, and then 1.2 g (8.6 mmol) of2-methyl azulene was added to the resultant solution. The obtainedreaction solution was stirred for 1.5 hours while the temperaturethereof was gradually raised to room temperature.

Thereafter, the reaction solution was cooled to 0° C. and mixed with 15μl (0.19 mmol) of 1-methylimidazole and then with 0.52 ml (4.3 mmol) ofdimethyldichlorosilane. After the reaction solution was stirred at roomtemperature for 1.5 hours, dilute hydrochloric acid was added thereto toterminate the reaction. The reaction solution was separated into organicand aqueous phases, and the organic phase was concentrated under areduced pressure. After dichloromethane was added to the concentratedorganic phase, the mixture was dried with magnesium sulfate and stirredunder a reduced pressure to remove the solvent. The thus-obtainedproduct was purified by a silica gel column chromatography (a mixedsolvent: dichloromethane and n-hexane), thereby obtaining 2.1 g of anamorphous solid product.

Next, 1.27 g of the thus-obtained amorphous solid product was dissolvedin 15 ml of diethyl ether. 2.8 ml of an n-hexane solution containing 4.5mmol of n-butyl lithium (1.66 M) was dropped into the diethyl ethersolution at −78° C. After completion of the dropping, the reactionsolution was stirred for 12 hours while the temperature thereof wasgradually raised to room temperature. After the reaction solution wasstirred under a reduced pressure to remove the solvent, 5 ml of a mixedsolvent of toluene and diethyl ether (40:1) was added thereto. Aftercooling to −78° C., the reaction solution was mixed with 0.53 (2.3 mmol)g of zirconium tetrachloride and the temperature thereof was immediatelyraised to room temperature, followed by stirring at room temperature for4 hours. The obtained reaction solution was filtered through celite toseparate a solid component therefrom. The thus-obtained solid componentwas washed with 3 ml of toluene to recover a solid reaction product. Therecovered solid reaction product was extracted with dichloromethane. Theextract was stirred under a reduced pressure to remove the solvent,thereby obtaining 906 mg of a racemic and meso mixture ofdimethylsilylene bis[{1,1′-(2-methyl-4-(4-chlorophenyl-4-hydroazulenyl}]zirconium dichloride (yield: 56%).

The chemical shifts of ¹H-NMR of the above-obtained racemic and mesomixture are as follows.

300 MHz, C₆D₆ (ppm) 0.45 (s, meso SiMe), 0.50 (s, racemic SiMe), 0.57(s, meso SiMe), 1.88 (s, meso 2-Me), 1.96 (s, racemic 2-Me), 5.17 (br s,racemic 4-H), 5.22 (br s, meso 4-H), 5.6-6.1 (m, —CH═), 6.65-6.8 (m,—CH═), 7.1-7.40 (m, —CH═)

(b) Purification of Racemic Compound

Further, 900 mg of the above-produced racemic and meso mixture wasdissolved in 20 ml of dichloromethane and irradiated with light for 40minutes by a 100 W high-pressure mercury vapor lamp to enhance apercentage of the racemic compound in the mixture. Thereafter, insolublecomponents were removed from the solution by filtration, and then therecovered filtrate was concentrated, dried and solidified. Next, thethus-obtained solid component was mixed with 22 ml of toluene whilestirring and then allowed to stand, followed by removing the supernatanttherefrom. Such purifying operations were repeated four times, and theobtained solid residue was dried to obtain 275 mg of a racemic compoundof dimethylsilylenebis[{1,1′-(2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride.

The chemical shifts of ¹H-NMR of the above-obtained racemic compound areas follows.

300 MHz, CDCl₃ (ppm) 0.95 (s, 6H, SiMe), 2.13 (s, 6H, 2-Me), 4.82-4.85(br d, 2H), 5.70-5.78 (m, 2H), 5.83-5.92 (m, 4H), 6.03-6.12 (m, 2H),6.70 (d, J=12 Hz, 2H), 7.1-7.35 (m, 8H, —CH═)

(2) Polymerization of Propylene Using Methylalumoxane as Co-catalyst

4 mmol (calculated as Al atom) of triethylaluminum (“MMAO”, produced byTOSOH AKZO CORP.) and 0.29 mg of the above-obtained racemic compoundwere charged into a 2-liter stirring-type autoclave. Further, theautoclave was charged with 1,500 ml of propylene. The content of theautoclave was heated to 70° C. to conduct the polymerization ofpropylene for one hour, thereby obtaining 72 g of polypropylene. As aresult of the measurements, it was confirmed that the complex activitywas 24.9×10⁴, and the obtained polypropylene had a melting point (Tm) of150.4° C., a melt flow rate (MFR) of 1.1, a weight-average molecularweight (Mw) of 3.6×10⁵ and a Q-value (Mw/Mn) of 3.0.

Example 13

Polymerization of Propylene Using Clay Minerals as Co-catalyst

(1) Chemical Treatment of Clay Minerals and Preparation of SolidCatalyst Component

The same procedure as defined in Example 11(2) was conducted to obtain amontmorillonite/toluene slurry containing montmorillonite in an amountof 33 mg/ml.

(2) Polymerization of Propylene

0.25 mmol (calculated as Al atom) of triisobutylaluminum (produced byTOSOH AKZO CORP.) was charged into a 1-liter stirring-type autoclave.Separately, 1.09 mg of the racemic compound obtained in Example 12(1)was diluted with toluene, and then charged into a catalyst feederequipped with a safety rupture disc. Further, the above-prepared slurrycontaining 50 mg of montmorillonite and 0.15 mmol (calculated as Alatom) of triisobutylaluminum were charged into the autoclave.Thereafter, 700 ml of propylene was introduced into the autoclave andthe safety rupture disc of the catalyst feeder was broken at roomtemperature. After the content of the autoclave was heated to 80° C.,the polymerization of propylene was conducted at that temperature forone hour, thereby obtaining 131.3 g of polypropylene. As a result of themeasurements, it was confirmed that the catalyst activity was 3,000 andthe complex activity was 13.5×10⁴, and the obtained polypropylene had amelting point (Tm) of 149.2° C., a melt flow rate (MFR) of 5.8, aweight-average molecular weight (Mw) of 2.4×10⁵ and a Q-value (Mw/Mn) of2.5.

Example 14

(1) Synthesis of dimethylsilylenebis[1,1′-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}]zirconium dichloride

The same procedure as defined in Example 12(1)(a) was conducted exceptthat 1.35 g of 1-bromo-4-trifluoromethyl benzene was used instead of1.15 g of 1-bromo-4-chlorobenzene in Example 12(1)(a), to obtain 1.16 gof an amorphous solid product.

Using the above-produced amorphous solid product, 2.2 ml of an n-hexanesolution of n-butyl lithium (1.66M) and 0.42 g (1.8 mmol) of zirconiumtetrachloride, the same procedure as defined in Example 12(1)(a) wasconducted, thereby obtaining 0.36 g of a yellow solid product. As aresult of ¹H-NMR analysis, the yellow solid product was identified to bea racemic and meso mixture of dimethylsilylenebis[1,1′-{2-methyl-4-(4-trifluoromethyl phenyl)-4-hydroazulenyl}]zirconium dichloride. The yield of the product was 15%.

(2) Polymerization of Propylene Using Methylalumoxane as Co-Catalyst

4 mmol (calculated as Al atom) of methylalumoxane (“MMAO” produced byTOSOH AKZO CORP.) and 0.6 mg of the above-produced racemic and mesomixture were charged into a 2-liter stirring-type autoclave. Further,1,500 ml of propylene was introduced into the autoclave. After thecontent of the autoclave was heated to 70° C., the polymerization ofpropylene was conducted at that temperature for one hour, therebyobtaining 50 g of polypropylene. As a result of the measurements, it wasconfirmed that the complex activity was 8.3×10⁴, and the obtainedpolypropylene had a melting point (Tm) of 153.2° C. and a melt flow rate(MFR) of 1.0.

Example 15

(1) Synthesis of dimethylsilylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride

(a) Synthesis of Racemic and Meso Mixture

10 ml of a pentane solution containing 16.4 mmol of t-butyl lithium(1.64 M) was dropped into a solution prepared by dissolving 0.90 ml (8.2mmol) of 1-bromo-4-fluorobenzene in a mixed solvent composed of 10 ml ofn-hexane and 10 ml of diethyl ether, at −78° C. The obtained solutionwas stirred at −78° C. for 15 minutes, and then at −10° C. for 45minutes. Thereafter, the solution was mixed with 1.05 g (7.37 mmol) of2-methyl azulene to react these components with each other. Theresultant reaction solution was stirred for one hour while thetemperature thereof was gradually raised to room temperature.Thereafter, the reaction solution was cooled to 0° C., and mixed with 10ml of tetrahydrofuran. Further, the reaction solution was mixed with 16μl (0.20 mmol) of 1-methylimidazole and 0.45 ml (3.7 mmol) ofdichlorodimethyl silane. After the reaction solution was stirred at roomtemperature for one hour, dilute hydrochloric acid was added thereto toterminate the reaction. The solution was separated into organic andaqueous phases, and the thus-separated organic phase was concentratedunder a reduced pressure and dried with magnesium sulfate. The driedproduct was stirred under a reduced pressure to remove the solventremaining therein. The thus-obtained product was purified by a silicagel column chromatography (a mixed solvent: dichloromethane andn-hexane), thereby obtaining 2.1 g of an amorphous solid product.

Next, 1.55 g of the thus-obtained amorphous solid product was dissolvedin 15 ml of diethyl ether. 3.5 ml of an n-hexane solution containing 5.8mmol of n-butyl lithium (1.66 M) was dropped into the diethyl ethersolution at −78° C. After completion of the dropping, the reactionsolution was stirred for 12 hours while the temperature thereof wasgradually raised to room temperature. After the reaction solution wasstirred under a reduced pressure to remove the solvent, 6 ml of a mixedsolvent of toluene and diethyl ether (40:1) were added thereto. Aftercooling to −78° C., the solution was further mixed with 0.68 g (2.9mmol) of zirconium tetrachloride and the temperature thereof wasimmediately raised to room temperature, followed by stirring at roomtemperature for 4 hours. The obtained reaction solution was mixed with30 ml of dichloromethane and filtered through celite. 25 ml of n-hexanewas added to the obtained filtrate, thereby obtaining, as a depositedproduct, 1.0 g of a racemic and meso mixture of dimethylsilylenebis[1,1′-{2-methyl-4-(4-fluorophenyl-4-hydroazulenyl}] zirconiumdichloride (yield: 50%).

The chemical shifts of ¹H-NMR of the above-obtained racemic and mesomixture are as follows.

300 MHz, C₆D₆ (ppm) 0.45 (s, meso SiMe), 0.51 (s, racemic SiMe), 0.58(s, meso SiMe), 1.89 (s, meso 2-Me), 1.97 (s, racemic 2-Me), 5.20 (br s,racemic 4-H), 5.28 (br s, meso 4-H), 5.6-6.2 (m, —CH═), 6.75-7.4 (m,—CH═)

(b) Purification of Racemic Compound

Next, 333 mg of the above-produced racemic and meso mixture wassuspended in 20 ml of dichloromethane and irradiated for 10 minutes by a100 W high-pressure mercury vapor lamp to enhance a percentage of theracemic compound in the mixture. Thereafter, insoluble components wereremoved from the solution by filtration, and the recovered filtrate wasconcentrated, dried and solidified. Next, the thus-obtained solidcomponent was mixed with 4 ml of toluene while stirring and then allowedto stand, followed by removing the supernatant therefrom. Such purifyingoperations were repeated three times, and the obtained solid residue waswashed two times with hexane and then dried, thereby obtaining 115 mg ofa racemic compound of dimethylsilylenebis[1,1′-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconiumdichloride.

The chemical shifts of ¹H-NMR of the above-obtained racemic compound areas follows.

300 MHz, CDCl₃ (ppm) 0.95 (s, 6H, Si—Me), 2.14 (s, 6H, 2-Me), 4.84 (br,2H, 4-H), 5.72-5.90 (m, 6H), 6.05-6.10 (m, 2H), 6.72 (d, J=12 Hz, 2H),6.95-7.05 (m, 4H, —CH═), 7.32-7.40 (m, 4H, —CH═)

(2) Polymerization of Propylene Using Methylalumoxane as Co-catalyst

The same procedure as defined in Example 12(2) was conducted except that0.29 mg of the racemic compound obtained in the above item (1) was usedinstead of the racemic compound obtained in Example 12(1), to obtain 30g of polypropylene. As a result of the measurements, it was confirmedthat the complex activity was 10.3×10⁴, and the obtained polypropylenehad a melting point (Tm) of 149.7° C., a melt flow rate (MFR) of 1.3, aweight-average molecular weight (Mw) of 3.4×10⁵ and a Q-value (Mw/Mn) of2.3.

Example 16

Polymerization of Propylene Using Clay Minerals as Co-catalyst

The same procedure as defined in Example 13(2) was conducted except that1.035 mg of the racemic compound obtained in Example 15 was used insteadof the racemic compound obtained in Example 13(1), to obtain 154 g ofpolypropylene. As a result of the measurements, it was confirmed thatthe catalytic activity was 3080 and the complex activity was 14.2×10⁴,and the obtained polypropylene had a melting point (Tm) of 148.0° C., amelt flow rate (MFR) of 6.9, a weight-average molecular weight (Mw) of2.2×10⁵ and a Q-value (Mw/Mn) of 2.4.

Example 17

(1) Synthesis of dimethylsilylenebis[1,1′-{2-methyl-4-(3-chlorophenyl)-4-hydroazulenyl}] hafniumdichloride

(a) Synthesis of Racemic and Meso Mixture

18.7 ml of a pentane solution containing 30.65 mmol of t-butyl lithium(1.64 M) was dropped into a solution prepared by dissolving 1.8 ml(15.32 mol) of 1-bromo-3-chlorobenzene in a mixed solvent composed of 20ml of n-hexane and 20 ml of diethyl ether, at −78° C. The resultantsolution was stirred at −5° C. for 1 hour, and then mixed with 1.96 g(13.79 mmol) of 2-methylazulene to react these components with eachother. The obtained reaction solution was stirred for 1.25 hours whilethe temperature thereof was gradually raised to room temperature.Thereafter, the reaction solution was cooled to 0° C., and mixed with 20ml of tetrahydrofuran and 30 μl (0.38 mmol) of 1-methylimidazole andthen with 0.84 ml (6.9 mmol) of dichlorodimethyl silane. After thereaction solution was stirred at room temperature for 1.5 hours, dilutehydrochloric acid was added thereto to terminate the reaction. Thereaction solution was separated into organic and aqueous phases, and theorganic phase was concentrated under a reduced pressure. Afterdichloromethane was added to the concentrated organic phase, the mixturewas dried with magnesium sulfate and stirred under a reduced pressure toremove the solvent, thereby obtaining an amorphous crude reactionproduct.

Next, the thus-obtained amorphous crude reaction product was dissolvedin 20 ml of dry diethyl ether. 8.6 ml of an n-hexane solution containing13.8 mmol of n-butyl lithium (1.6 M) was dropped into the diethyl ethersolution at −78° C. After completion of the dropping, the reactionsolution was stirred for 12 hours while the temperature thereof wasgradually raised to room temperature. After the reaction solution wasstirred under a reduced pressure to remove the solvent, 15 ml of a mixedsolvent of toluene and diethyl ether (40:1) was added thereto. Aftercooling to −78° C., the reaction solution was mixed with 2.2 g (6.9mmol) of hafnium tetrachloride and the temperature thereof wasimmediately raised to room temperature, followed by stirring at roomtemperature for 5 hours. The obtained reaction solution was filteredthrough celite to separate a solid component therefrom. Thethus-obtained solid component was washed with 5 ml of toluene and 4 mlof hexane to recover a solid reaction product. The recovered solidreaction product was extracted with 40 ml of dichloromethane. Theextract was stirred under a reduced pressure to remove the solvent,thereby obtaining 571 mg of a racemic and meso mixture ofdimethylsilylene bis[1,1′-{2-methyl-4-(3-chlorophenyl-4-hydroazulenyl}]hafnium dichloride (yield: 10%).

(b) Purification of Racemic Compound

Further, 571 mg of the above-produced racemic and meso mixture wasdissolved in 15 ml of dichloromethane and irradiated with light for 15minutes by a 100 W high-pressure mercury vapor lamp to enhance apercentage of the racemic compound in the mixture. Thereafter, insolublecomponents were removed from the solution by filtration, and then therecovered filtrate was concentrated, dried and solidified. Next, thethus-obtained solid component was mixed with 5 ml of toluene whilestirring, followed by filtration of the resultant mixture through frit.The obtained solid residue was washed with 3 ml of toluene and 4 ml ofhexane, and then dried under a reduced pressure, thereby obtain 290 mgof a racemic compound of dimethylsilylenebis[1,1′-{2-methyl-4-(3-chlorophenyl)-4-hydroazulenyl}] hafniumdichloride.

The chemical shifts of ¹H-NMR of the above-obtained racemic compound areas follows.

300 MHz, CDCl₃ (ppm) 0.95 (s, 6H, SiMe), 2.22 (s, 6H, 2-Me), 4.93-4.97(br d, 2H), 5.70-5.90 (m, 6H), 5.97-6.05 (m, 2H), 6.75 (d, 2H),7.15-7.27 (m, 6H, arom), 7.33 (s, 2H, arom)

(2) Polymerization of Propylene Using Clay Minerals as Co-catalyst

The same procedure as defined in Example 13(2) was conducted except that1.22 mg of the racemic compound obtained in the above item (1) was usedinstead of the racemic compound obtained in Example 12(1), to obtain 110g of polypropylene. As a result of the measurements, it was confirmedthat the complex activity was 9.0×10⁴, the catalytic activity was 2200,and the obtained polypropylene had a melting point (Tm) of 152.4° C. anda melt flow rate (MFR) of 0.5.

Example 18

(1) Synthesis of dimethylsilylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] hafniumdichloride

29 ml of a pentane solution containing 47.0 mmol of t-butyl lithium(1.64 M) was dropped into a solution prepared by dissolving 4.5 g (23.53mmol) of 1-bromo-4-chlorobenzene in a mixed solvent composed of 30 ml ofn-hexane and 30 ml of diethyl ether, at −78° C. The resultant solutionwas stirred at −5° C. for 1.5 hours, and then mixed with 3.0 g (21.2mmol) of 2-methyl azulene to react these components with each other. Thereaction solution was stirred for 1 hour while the temperature thereofwas gradually raised to room temperature.

Thereafter, the reaction solution was cooled to −5° C., and then mixedwith 40 μl (0.47 mmol) of 1-methylimidazole and then with 1.28 ml (10.59mmol) of dichlorodimethyl silane. After the reaction solution wasstirred at room temperature for 1.5 hours, dilute hydrochloric acid wasadded thereto to terminate the reaction. The reaction solution wasseparated into organic and aqueous phases, and the organic phase wasconcentrated under a reduced pressure. After the solvent is removed, theobtained product was purified by a silica gel column chromatography (amixed solvent; dichloromethane and n-hexane), thereby obtaining 2.74 gof an amorphous solid product.

Next, the thus-obtained reaction product was dissolved in 20 ml of drydiethyl ether. 6.3 ml of an n-hexane solution containing 9.72 mmol ofn-butyl lithium (1.54 M) was dropped into the diethyl ether solution at−78° C. After completion of the dropping, the reaction solution wasstirred for 12 hours while the temperature thereof was gradually raisedto room temperature. Thereafter, the reaction solution was stirred undera reduced pressure to remove the solvent, and then mixed with 15 ml of amixed solvent of dry toluene and dry diethyl ether (40:1). After coolingto −78° C., the reaction solution was mixed with 1.56 g (4.86 mmol) ofhafnium tetrachloride and the temperature thereof was immediately raisedto room temperature, followed by stirring at room temperature for 4hours. The obtained reaction solution was filtered through celite toseparate a solid component therefrom. The thus-obtained solid componentwas extracted with 90 ml of dichloromethane. The extract was subjectedto distillation to remove the solvent therefrom, thereby obtaining 320mg of a racemic compound of dimethylsilylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] hafniumdichloride (yield: 7%)

The chemical shifts of ¹H-NMR of the above-obtained racemic compound areas follows.

300 MHz, CDCl₃ (ppm) δ0.95 (s, 6H, SiMe₂), 2.21 (s, 6H, 2-Me), 4.92-4.96(br d, 2H), 5.70-6.15 (m, 8H), 6.78 (d, 2H), 7.28 (s, 8H, arom)

(2) Polymerization of propylene Using Methylalumoxane as Co-catalyst

Polymerization of Propylene

4 mmol (calculated as Al atom) of methylalumoxane (“MMAO” produced byTOSOH AKZO CORP.) and a toluene solution containing 0.65 mg of a racemiccompound of dimethylsilylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] hafniumdichloride obtained in the above item (1) were charged into a 2-literstirring-type autoclave. Further, 1,500 ml of propylene was introducedinto the autoclave. The content of the autoclave was heated to 70° C.,and the polymerization of propylene was conducted for one hour to obtain8 g of polypropylene. As a result of the measurements, it was confirmedthat the complex activity was 1.23×10⁴, and the obtained polypropylenehad a melting point (Tm) of 154.4° C., a melt flow rate (MFR) of 0.07, aweight-average molecular weight (Mw) of 14×10⁵ and a Q-value (Mw/Mn) of4.0.

Example 19

Polymerization of Propylene

The same procedure as defined in Example 6(2) was conducted except thatthe racemic compound of dimethylsilylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] hafniumdichloride obtained in Example 18(1) was used as the component (A), toobtain 146 g of polypropylene. As a result of the measurements, it wasconfirmed that the catalytic activity was 2900, the complex activity was12.0×10⁴, and the obtained polypropylene had a melting point (Tm) of150.6° C., a melt flow rate (MFR) of 0.4, a weight-average molecularweight (Mw) of 5.6×10⁵ and a Q-value (Mw/Mn) of 3.1.

Example 20

(1) Chemical Treatment and Granulation of Clay Minerals

3 Kg of commercially available montmorillonite (“KUNIPIA F” produced byKUNIMINE INDUSTRIES CO., LTD.) was pulverized by a vibrating mill anddispersed in 16 liters of 3% aqueous solution of sulfuric acid. Thedispersion was mixed with 2.1 Kg of magnesium sulfate, followed bystirring at 90° C. for 3 hours. Thereafter, the dispersion was filteredto separate a solid component therefrom. The thus-obtained solidcomponent was washed with water to adjust the pH thereof to not lessthan 5. Successively, after the solid content of the obtained slurry wasadjusted to 15%, the slurry was sprayed by means of a spray drier toconduct granulation of the solid component. The thus-obtained particleswere of a spherical shape.

10.0 g of the chemically treated montmorillonite obtained in the abovewas charged into a 200 ml flask and subjected to heating and desiccationtreatment at 300° C. for 2 hours under a reduced pressure, therebyobtaining a component (B).

(2) Preparation of Solid Catalyst Component and Pre-Polymerization ofPropylene

400 ml of heptane was introduced into a 1-liter stirring-type autoclaveand maintained at 40° C.

Separately, 10 g of the component (B) obtained in the above item (1) wasdispersed in 40.2 ml of toluene. The dispersion was mixed with 79.8 mlof a dilute toluene solution containing triethylaluminum in an amountcorresponding to 60 mmol. After these components were contacted witheach other at room temperature for one hour, the supernatant was removedfrom the mixture, and the obtained solid residue was washed with tolueneand then charged into the autoclave.

Next. 48.8 ml of a toluene solution containing dimethylsilylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] hafniumdichloride obtained in Example 18(1) in an amount corresponding to 0.10mmol was charged into the autoclave. Further, 4.96 ml of a dilutetoluene solution containing triisobutylaluminum in an amountcorresponding to 4 mmol was dropped into the autoclave and thenpropylene was fed thereinto to initiate the polymerization(pre-polymerization) of propylene. The polymerization of propylene wascontinued for 15 minutes while maintaining the propylene pressure withinthe autoclave at 5 kgf/cm²G. After completion of the polymerization, thepolymerized slurry was taken out of the autoclave and the supernatantwas removed therefrom to obtain a solid residue. The solid residue wasdried at 40° C. for 3 hours under a reduced pressure, thereby obtaininga dry catalyst. The amount of the polymer obtained by thepre-polymerization was 3.1 g based on one gram of the component (B).

(3) Polymerization of Propylene

0.4 g of triisobutylaluminum and 1.5 liters of propylene were chargedinto a 3-liter stirring-type autoclave. While maintaining the content ofthe autoclave at 30° C., 30 mg of the dry catalyst (as the amount of thecomponent (B) except for the pre-polymerized product) obtained in theabove item (2) was introduced under pressure into the autoclave. Next,the content of the autoclave was heated to 75° C. to conduct thepolymerization of propylene for one hour. After completion of thepolymerization, unreacted propylene was purged to recover polypropyleneproduced. The results are shown in Table 3.

Examples 21 and 22 Polymerization of Propylene

The same procedure as defined in Example 20(1)-(3) was conducted exceptthat after introduction of the dry catalyst in Example 20(3), hydrogenwas introduced into the autoclave in amounts shown in Table 3. Theresults are shown in Table 3.

Example 23

Polymerization of Propylene

The same procedure as defined in Example 20(1)-(3) was conducted exceptthat the amount of the dry catalyst charged into the autoclave inExample 20(3) was changed to 15 mg (as the amount of the component (B)except for the pre-polymerized product). The results are shown in Table3.

Example 24 Random Copolymerization of Propylene and Ethylene

The same procedure as defined in Example 20(1)-(3) was conducted exceptthat the amount of the dry catalyst charged into the autoclave inExample 20(3) was changed to 15 mg (as the amount of the component (3)except for the pre-polymerized product), and further 1.5 liters ofpropylene and 45 g of ethylene were introduced into the autoclave. Theresults are shown in Table 3.

Examples 25 to 27

The same procedure as defined in Example 20(1)-(3) was conducted exceptthat the respective conditions as defined in Example 20 were changed asfollows. The results are shown in Table 3.

(1) Preparation of Solid Catalyst Component and Pre-polymerization ofPropylene

The dry catalysts were prepared under the same conditions as defined inExample 20(2) except that compounds shown in Table 3 were used as thecomponent (A).

(2) Polymerization of Propylene

The polymerization of propylene was conducted under the same conditionsas defined in Example 20(3) except that 50 mg of each of the drycatalysts (as the amount of the component (B) except for thepre-polymerized product) obtained in the above (1) was used.

Comparative Example 3

(1) Preparation of Solid Catalyst Component and Pre-Polymerization ofPropylene

The dry catalysts were prepared under the same conditions as defined inExample 20(2) except that 10 g of dimethylsilylenebis{1,1′-(2-methyl-4-phenylhydroazulenyl)} zirconium dichloride was usedas the compound (A) and 10 g of methylalumoxane supported by silicacarrier (MAO on SiO₂ by WITCO Co.,Ltd., Al atom content: 23 wt %) wasused as the compound (B) instead of the chemical-treated clay mineral.The amount of the polymer obtained by the pre-polymerization was 2.8 gbased on one gram of the MAO on SiO₂.

(2) Polymerization of Propylene

The same procedure as defined in Example 20(3) was conducted except thatthe catalyst component prepared in the above item (1) was used insteadof the catalyst used in Example 20(3). The results are shown in Table 3.

TABLE 3 Amount of Component Amount Amount solid (C): of of Com- catalysttriisobutyl hydrogen ethylene ponent component aluminum suppliedsupplied (A) used (mg) (mg) (ml) (g) Ex. 20 a 30 400 0 0 Ex. 21 a 30 40042.5 0 Ex. 22 a 30 400 136 0 Ex. 23 a 15 400 0 0 Ex. 24 a 15 400 0 45 Ex. 25 b 50 400 0 0 Ex. 26 c 50 400 0 0 Ex. 27 d 50 400 0 0 Comp. d 50400 0 0 Ex. 3 Note: a: dimethylsilylenebis{1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] hafniumdichloride; b: dimethylsilylenebis[1,1′-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconiumdichloride; c: dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)] hafnium dichloride; d:dimethylsilylene bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)] zirconiumdichloride; Melting Catalytic Complex point MFR activity activity (° C.)(g/10 min) Example 20 1900 23.4 153.1 0.19 Example 21 5600 68.9 153.71.87 Example 22 9400 115.7 155.0 16.1 Example 23 1600 19.7 154.0 0.076Example 24 9700 119.4 127.7 0.038 Example 25 1430 19.7 149.3 4.6 Example26 3100 41.7 150.9 0.84 Example 27 2020 30.8 147.7 6.2 Comparative  71010.8 146.7 7.6 Example 3 Mw Q (× 10⁵) (Mw/Mn) Bulk density (g/ml)Example 20 — — 0.38 Example 21 — — 0.38 Example 22 — — 0.41 Example 23 —— 0.39 Example 24 — — 0.38 Example 25 3.2 3.4 0.48 Example 26 5.8 3.90.48 Example 27 2.8 3.0 0.47 Comparative 2.5 2.8 0.37 Example 3

Example 28

(1) Synthesis of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl} zirconiumdichloride

4.9 ml of a cyclohexane/diethyl ether solution containing 5.2 mmol ofphenyl lithium (1.08 M) was dropped into 20 ml of a hexane solutioncontaining 0.97 g (5.2 mmol) of 2-methyl-5-isopropylazulene, at 0° C.The resultant solution was stirred for 1 hour while the temperaturethereof was gradually raised to room temperature. Thereafter, thereaction solution was cooled to 0° C., and mixed with 20 ml oftetrahydrofuran and 12 μl (0.15 mmol) of dimethylaminopyridine and thenwith 0.34 g (2.6 mmol) of dichlorodimethylsilane. After the reactionsolution was stirred at room temperature for 2 hours, dilutehydrochloric acid was added thereto to terminate the reaction. Thereaction solution was separated into organic and aqueous phases, and theorganic phase was extracted with hexane, dried with magnesium sulfateand stirred under a reduced pressure to remove the solvent. The obtainedproduct was purified by a silica gel column chromatography (a mixedsolvent: dichloromethane and n-hexane), thereby obtaining 1.4 g of darkgreen powder as a reaction product.

Next, 1.4 g of the thus-obtained reaction product was dissolved in 15 mlof diethyl ether. 3.2 ml of an n-hexane solution containing 4.9 mmol ofn-butyl lithium (1.54 M) was dropped into the diethyl ether solution at−78° C. After completion of the dropping, the reaction solution wasstirred for 2 hours while the temperature thereof was gradually raisedto 0° C. After the reaction solution was stirred under a reducedpressure to remove the solvent, 23 ml of a mixed solvent of toluene anddiethyl ether (20:1) was added thereto. After cooling to −78° C., thereaction solution was mixed with 0.57 g (2.4 mmol) of zirconiumtetrachloride and the temperature thereof was immediately raised to 0°C., followed by stirring at 0° C. for one hour. Further, the temperatureof reaction solution was raised to room temperature and stirred at roomtemperature for 6 hours. The obtained reaction solution was filteredthrough celite to separate a solid component therefrom. Thethus-separated solid component was washed with 3 ml of toluene torecover a solid product. The recovered solid product was extracted withdichloromethane. The extract was stirred under a reduced pressure toremove the solvent, thereby obtaining 0.11 g of a racemic and mesomixture of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl}] zirconiumdichloride (yield: 6%).

The chemical shifts of ¹H-NMR of the above-obtained racemic and mesomixture are as follows.

300 MHz, C₆D₆ (ppm) 0.55 (s, meso SiMe), 0.57 (s, racemic SiMe), 0.60(s, meso SiMe), 1.00 (d, iPr-Me), 1.12 (d, iPr-Me), 1.88 (s, 2-Me), 1.90(s, 2-Me), 3.1 (m, iPr-CH), 5.26 (br s, 4-H), 5.28 (br s, 4-H), 5.7-5.9(m, —CH═), 7.0-7.5 (m, —CH═)

(2) Polymerization of Propylene Using Methylalumoxane as Co-catalyst

4 mmol (calculated as Al atom) of methylalumoxane (“MMAO” produced byTOSOH AXZO CORP.) was charged into a 2-liter stirring-type autoclave.Separately, 0.3 mg of the above-produced racemic and meso mixture wasdiluted with toluene, and then charged into a catalyst feeder equippedwith a safety rupture disc. Thereafter, 1,500 ml of propylene wasintroduced into the autoclave and the safety rupture disc of thecatalyst feeder was broken at room temperature. After the content of theautoclave was heated to 70° C., the polymerization of propylene wasconducted at that temperature for one hour, thereby obtaining 32 g ofpolypropylene. As a result of the measurements, it was confirmed thatthe complex activity was 1.1×10⁵, and the obtained polypropylene had amelting point (Tm) of 152.6° C., a melt flow rate (MFR) of 1.4, aweight-average molecular weight (Mw) of 3.6×10⁵ and a Q-value (Mw/Mn) of3.5.

Example 29

Polymerization of α-Olefin Using Clay Minerals as Co-catalyst

(1) Chemical Treatment of Clay Minerals and Preparation of SolidCatalyst Component

The same procedure as defined in Example 11(2) was conducted to obtain amontmorillonite/toluene slurry having a montmorillonite content of 33mg/ml.

(2) Polymerization of Propylene

0.5 mmol (calculated as Al atom) of triisobutylaluminum (produced byTOSOH AKZO CORP.) was charged into a 2-liter stirring-type autoclave.Separately, 1.8 mg of the racemic and meso mixture obtained in Example28(1) was diluted with toluene, and then charged into a catalyst feederequipped with a safety rupture disc. Further, the above-prepared slurrycontaining 100 mg of montmorillonite and 0.3 mmol (calculated as Alatom) of triisobutylaluminum were charged into the catalyst feeder.Thereafter, 1,500 ml of propylene was introduced into the autoclave andthe safety rupture disc of the catalyst feeder was broken at roomtemperature. After the content of the autoclave was heated to 80° C.,the polymerization of propylene was conducted at that temperature forone hour, thereby obtaining 37 g of polypropylene. As a result of themeasurements, it was confirmed that the catalyst activity was 370, thecomplex activity was 2.1×10⁴, and the obtained polypropylene had amelting point (Tm) of 146.0° C., a melt flow rate (MFR) of 143, aweight-average molecular weight (Mw) of 1.4×10⁵ and a Q-value (Mw/Mn) of2.2.

Example 30

(1) Synthesis of dimethylsilylenebis{1,1′-(2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride

7.2 ml of a cyclohexane/diethyl ether solution containing 7.8 mmol ofphenyl lithium (1.08 M) was dropped into 20 ml of a hexane solutioncontaining 1.54 g (7.8 mmol) of 2-ethyl-5-isopropyl azulene, at 0° C.The resultant solution was stirred for 1 hour while the temperaturethereof was gradually raised to room temperature. Thereafter, thereaction solution was cooled to 0° C., and mixed with 20 ml oftetrahydrofuran and 12 μl (0.15 mmol) of dimethylaminopyridine and thenwith 0.50 g (3.9 mmol) of dichlorodimethylsilane. After the reactionsolution was stirred at room temperature for 2 hours, dilutehydrochloric acid was added thereto to terminate the reaction. Thereaction solution was separated into organic and aqueous phases, and theorganic phase was extracted with hexane, dried with magnesium sulfateand stirred under a reduced pressure to remove the solvent, therebyobtaining 2.5 g of dark green powder as a reaction product.

Next, 2.5 g of the thus-obtained reaction product was dissolved in 30 mlof diethyl ether. 4.9 ml of an n-hexane solution containing 7.8 mmol ofn-butyl lithium (1.59 M) was dropped into the diethyl ether solution at−78° C. After completion of the dropping, the reaction solution wasstirred for 4 hours while the temperature thereof was gradually raisedto room temperature. After the reaction solution was stirred under areduced pressure to remove the solvent, 20 ml of a mixed solvent oftoluene and diethyl ether (20:1) was added thereto. After cooling to−78° C., the reaction solution was mixed with 0.91 g (3.9 mmol) ofzirconium tetrachloride and the temperature thereof was immediatelyraised to 0° C., followed by stirring at 0° C. for one hour. Further,the temperature of reaction solution was raised to room temperature andstirred at room temperature for 11 hours. The obtained reaction solutionwas filtered through celite to separate a solid component therefrom. Thethus-obtained solid component was washed with 3 ml of toluene to recovera solid reaction product. The recovered solid reaction product wasextracted with dichloromethane. The extract was stirred under a reducedpressure to remove the solvent, thereby obtaining 0.4 g of a racemic andmeso mixture of dimethylsilylenebis{1,1′-(2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride (yield: 7%).

The chemical shifts of ¹H-NMR of the above-obtained racemic and mesomixture are as follows.

300 MHz, C₆D₆ (ppm) 0.58 (s, meso SiMe), 0.60 (s, racemic SiMe), 0.62(s, meso SiMe), 1.1 (m, iPr-Me, Et-Me), 1.92 (q, Et-CH₂), 1.98 (q,Et-CH₂), 3.2 (m, iPr-CH), 5.26 (br s, 4-H), 5.29 (br s, 4-H), 5.7-5.9(m, —CH═), 7.0-7.5 (m, —CH═)

(2) Polymerization of Propylene Using Methylalumoxane as Co-catalyst

4 mmol (calculated as Al atom) of methylalumoxane (“MMAO” produced byTOSOH AKZO CORP.) was charged into a 2-liter stirring-type autoclave.Separately, 0.3 mg of the above-produced racemic and meso mixture wasdiluted with toluene, and then charged into a catalyst feeder equippedwith a safety rupture disc. Thereafter, 1,500 ml of propylene wasintroduced into the autoclave and the safety rupture disc of thecatalyst feeder was broken at room temperature. After the content of theautoclave was heated to 70° C., the polymerization of propylene wasconducted at that temperature for one hour, thereby obtaining 52 g ofpolypropylene. As a result of the measurements, it was confirmed thatthe complex activity was 1.7×10⁵, and the obtained polypropylene had amelting point (Tm) of 155.5° C., a melt flow rate (MFR) of 0.2, aweight-average molecular weight (Mw) of 5.3×10⁵ and a Q-value (Mw/Mn) of3.8.

Example 31

Polymerization of Propylene Using Clay Minerals as Co-catalyst

0.25 mmol (calculated as Al atom) of triisobutylaluminum (produced byTOSOH AKZO CORP.) was charged into a 1-liter stirring-type autoclave.Separately, 0.8 mg of the racemic and meso mixture obtained in Example30(1) was diluted with toluene, and then charged into a catalyst feederequipped with a safety rupture disc. Further, 50 mg of thetriethylaluminum-treated montmorillonite obtained in Example 29(1) and0.15 mmol (calculated as Al atom) of triisobutylaluminum were chargedinto the catalyst feeder. Thereafter, 700 ml of propylene was introducedinto the autoclave and the safety rupture disc of the catalyst feederwas broken at room temperature. After the content of the autoclave washeated to 80° C., the polymerization of propylene was conducted at thattemperature for one hour, thereby obtaining 4 g of polypropylene. As aresult of the measurements, it was confirmed that the catalyst activitywas 76, the complex activity was 5.0×10³, and the obtained polypropylenehad a melting point (Tm) of 148.4° C., a weight-average molecular weight(Mw) of 1.5×10⁵ and a Q-value (Mw/Mn) of 2.8.

Example 32

(1) Synthesis of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl -4-hydroazulenyl)} zirconiumdichloride as component (A)

(a) Synthesis of 2-tosyl-4-isopropyltropolone

10.2 g (62.3 mmol) of hinokitiol was dissolved in 20 ml of pyridine. 20ml of a pyridine solution containing 12.1 g (63.5 mmol) of tosylchloride was added to the above-prepared solution at room temperature.The resultant reaction solution was extracted with toluene. An organicphase of the extract was dried with magnesium sulfate, and then thesolvent contained therein was removed under a reduced pressure, therebyobtaining 20.7 g of a mixture of 2-tosyl-4-isopropyltropolone and2-tosyl-6-isopropyltropolone.

(b) Synthesis of 1-methoxy carbonyl-6-isopropylcycloheptafuran-2-one

A sodium methoxide solution prepared from 100 ml of methanol and 2.1 g(94.3 mmol) of sodium was added to 100 ml of a methanol solutioncontaining 17.6 g (55.5 mmol) of the mixture obtained in the above item(a) and 10.8 ml (94.3 mmol) of dimethyl malonate at 0° C. The mixedsolution was stirred at 0° C. for one hour and then at room temperatureovernight. After the solvent contained in the mixed solution was removedunder a reduced pressure, the mixed solution was mixed with water andthen extracted with a mixed solvent composed of hexane and ethylacetate. An organic phase of the extract was dried with magnesiumsulfate, and the solvent was removed under a reduced pressure, therebyobtaining 12.2 g of a crude product of1-methoxycarbonyl-6-isopropylcycloheptafuran-2-one.

(c) Synthesis of 1-methoxycarbonyl-2-methyl-6-isopropylazulene

600 ml of acetone and 200 ml of diethyl amine were added to 12.2 g ofthe above-obtained crude product of1-methoxycarbonyl-6-isopropylcycloheptafuran-2-one. The mixture wassubjected to intermittent reflux for 15 hours while heating. Thereafter,the solvent contained in the mixture was removed under a reducedpressure. The resultant crude product was purified by a columnchromatography using a mixed solvent composed of hexane and ethylacetate (5:1) as an eluent solvent, thereby obtaining 3.93 g of1-methoxy arbonyl-2-methyl-6-isopropylazulene.

(d) Synthesis of 2-methyl-6-isopropylazulene

70 ml of phosphoric acid was added to 3.93 g (16.2 mmol) of1-methoxycarbonyl-2-methyl-6-isopropylazulene, and the mixture washeated at 100° C. for one hour. The resultant reaction solution wasadded to 300 ml of an aqueous solution containing 30 g of sodiumhydroxide and extracted with hexane. An organic phase of the extract wasdried with magnesium sulfate, and the solvent remaining therein wasremoved under a reduced pressure. The obtained crude product wasfiltered through silica gel. Further, the solvent contained in thefiltered solid component was removed, thereby obtaining 2.23 g of2-methyl-6-isopropylazulene (yield: 75%).

(e) Synthesis ofbis{1,1′-(2-methyl-4-phenyl-6-isopropyldihydroazulenyl)} dimethyl silane

A diethyl ether/cyclohexane solution containing 12.1 mmol (1.0 N) ofphenyl lithium was added to 40 ml of a hexane solution containing 2.08 g(11.3 mmol) of the above-produced 2-methyl-6-isopropylazulene at 0° C.The mixed solution was stirred at room temperature for 2 hours, and thenmixed with 30 ml of tetrahydrofuran at −10° C. Further, 0.68 ml (5.64mmol) of dichlorodimethylsilane was added to the mixed solution at −30°C., followed by stirring for one hour at room temperature and then for 2hours at 45° C. After the mixed solution was allowed to stand at roomtemperature overnight, an ammonium chloride aqueous solution was addedto the obtained reaction solution. After the reaction solution wasseparated into aqueous and organic phases and the organic phaseseparated was dried with magnesium sulfate, the solvent was removedunder a reduced pressure. The obtained crude product was purified by acolumn chromatography using a mixed solvent composed of hexane anddichloromethane (10:1 to 5:1) as an eluent solvent, thereby obtaining1.23 g of bis{1,1′-(2-methyl-4-phenyl-6-isopropyl-1,4-dihydroazulenyl)}dimethylsilane (yield: 38%).

(f) Synthesis of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconiumdichloride

A hexane solution containing 4.55 mmol (1.63 N) of n-butyl lithium wasadded to 20 ml of a diethyl ether solution containing 1.2 g (2.07 mmol)of the above-producedbis{1,1′-(2-methyl-4-phenyl-6-isopropyl-1,4-dihydroazulenyl)}dimethylsilane at −78° C. After the mixed solution was stirred at roomtemperature overnight, the solvent contained in the obtained product wasremoved. The resultant product was washed with hexane, dried andsolidified again. The obtained solid product was mixed with 20 ml oftoluene and 0.5 ml of diethyl ether to form a solution. 434 mg (1.89mmol) of zirconium tetrachloride was then added to the solution at −70°C.

The temperature of obtained reaction solution was gradually raised toroom temperature and stirred at room temperature overnight. Thereafter,the reaction solution was filtered through celite, and the solventcontained in the separated solid component was removed under a reducedpressure. The solid component was dissolved again in 1 ml ofdichloromethane and then mixed with 10 ml of hexane. At this time, noprecipitate was formed. The obtained solution was dried and solidifiedunder a reduced pressure, thereby obtaining 1.36 g of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconiumdichloride.

(2) Polymerization of Propylene

The same procedure as defined in Example 1(4) was conducted except thatthe above-produced dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconiumdichloride was used as the component (A), to obtain 120 g ofpolypropylene. As a result of the measurements, it was confirmed thatthe catalytic activity was 1200, the complex activity was 11.6×10⁴, andthe obtained polypropylene had a melting point (Tm) of 148.5° C., a meltflow rate (MFR) of 8.8, a weight-average molecular weight (Mw) of2.4×10⁵ and a Q-value (Mw/Mn) of 2.8.

Example 33

Polymerization of Propylene Using Methylalumoxane as Co-catalyst

4 mmol (calculated as Al atom) of methylalumoxane (“MMAO” produced byTOSOH AKZO CORP.) and 1 mg of dimethylsilylenebis{1,1′-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconiumdichloride produced in Example 32(1) were diluted with toluene, and thencharged into a 2-liter stirring-type autoclave. Thereafter, 1,500 ml ofpropylene was introduced into the autoclave. After the content of theautoclave was heated to 70° C., the polymerization of propylene wasconducted at that temperature for one hour, thereby obtaining 70.4 g ofpolypropylene. As a result of the measurements, it was confirmed thatthe complex activity was 7.0×10⁴, and the obtained polypropylene had amelting point (Tm) of 149.8° C., a melt flow rate (MFR) of 7.9, aweight-average molecular weight (Mw) of 2.6×10⁵ and a Q-value (Mw/Mn) of2.8.

Example 34

(1) Synthesis of dimethylsilylenebis{1,1′-(2-benzyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride

7.2 ml of a cyclohexane/diethyl ether solution containing 7.8 mmol ofphenyl lithium (1.08 M) was dropped into 35 ml of a hexane solutioncontaining 1.7 g (7.8 mmol) of 2-benzylazulene, at −5° C. The resultantsolution was stirred for 2 hour while the temperature thereof wasgradually raised to room temperature. Thereafter, the reaction solutionwas cooled to 0° C., and mixed with 35 ml of tetrahydrofuran and 0.016 gof 1-methylimidazole and then with 0.5 g (3.9 mmol) ofdichlorodimethylsilane. After the reaction solution was stirred at roomtemperature for 1 hour, dilute hydrochloric acid was added thereto toterminate the reaction. The reaction solution was separated into organicand aqueous phases, and the organic phase was extracted with ether,dried with magnesium sulfate and stirred under a reduced pressure toremove the solvent. The obtained product was purified by a silica gelcolumn chromatography (a mixed solvent: dichloromethane and n-hexane),thereby obtaining 1.5 g of dark green powder as a reaction product.

Next, 1.5 g of the thus-obtained reaction product was dissolved in 10 mlof diethyl ether. 2.9 ml of an n-hexane solution containing 46.4 mmol ofn-butyl lithium (1.59 M) was dropped into the diethyl ether solution at−78° C. After completion of the dropping, the reaction solution wasstirred for 4 hours while the temperature thereof was gradually raisedto room temperature. After the reaction solution was stirred under areduced pressure to remove the solvent, 15 ml of a mixed solvent oftoluene and diethyl ether (40:1) was added thereto. After cooling to−78° C., the reaction solution was mixed with 0.54 g (23.2 mmol) ofzirconium tetrachloride and the temperature thereof was immediatelyraised to room temperature, followed by stirring at room temperature for12 hours. The obtained reaction solution was filtered through celite inthe presence of a nitrogen stream to separate a solid componenttherefrom. The thus-obtained solid component was washed with toluene andstirred under a reduced pressure to remove the solvent, therebyobtaining 1.4 g of a racemic and meso mixture of dimethylsilylenebis{1,1′-(2-benzyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride(yield: 74%).

The chemical shifts of ¹H-NMR of the above-obtained racemic and mesomixture are as follows.

300 MHz, C₆D₆ (ppm) 0.83 (s, meso SiMe), 0.92 (s, racemic SiMe), 1.05(meso SiMe), 3.75 (d, racemic benzyl CH₂), 3.90 (d, meso benzyl CH₂),4.04 (d, racemic and meso benzyl CH₂), 4.99 (d, racemic 4-H), 5.06 (d,meso 4-H), 5.8-6.2 (m, —CH═), 6.8-7.6 (m, —CH═)

(2) Polymerization of Propylene Using Methylalumoxane as Co-catalyst

2 mmol (calculated as Al atom) of methylalumoxane (“MMAO” produced byTOSOH AKZO CORP.) was charged into a 1-liter stirring-type autoclave.Separately, 0.32 mg of the above-produced racemic and meso mixture wasdiluted with toluene, and then charged into a catalyst feeder equippedwith a safety rupture disc. Thereafter, 700 ml of propylene wasintroduced into the autoclave and the safety rupture disc of thecatalyst feeder was broken at room temperature. After the content of theautoclave was heated to 70° C., the polymerization of propylene wasconducted at that temperature for one hour, thereby obtaining 10 g ofpolypropylene. As a result of the measurements, it was confirmed thatthe complex activity was 3.1×10⁴, and the obtained polypropylene had amelting point (Tm) of 156.6° C., a melt flow rate (MFR) of 400, aweight-average molecular weight (Mw) of 0.8×10⁵ and a Q-value (Mw/Mn) of3.2.

Example 35

Polymerization of Propylene Using Clay Minerals as Co-catalyst

(1) Chemical Treatment of Clay Minerals and Preparation of SolidCatalyst Component

The same procedure as defined in Example 11(2) was conducted to obtain amontmorillonite/toluene slurry having a montmorillonite content of 33mg/ml.

(2) Polymerization of Propylene

0.25 mmol (calculated as Al atom) of triisobutylaluminum (produced byTOSOH AKZO CORP.) was charged into a 1-liter stirring-type autoclave.Separately, 2.4 mg of the racemic and meso mixture obtained in Example34(1) was diluted with toluene, and then charged into a catalyst feederequipped with a safety rupture disc. Further, the above-prepared tolueneslurry containing 50 mg of montmorillonite and 0.15 mmol (calculated asAl atom) of triisobutylaluminum were charged into the catalyst feeder.Thereafter, 700 ml of propylene was introduced into the autoclave andthe safety rupture disc of the catalyst feeder was broken at roomtemperature. After the content of the autoclave was heated to 80° C.,the polymerization of propylene was conducted at that temperature forone hour, thereby obtaining 0.8 g of polypropylene. As a result of themeasurements, it was confirmed that the catalyst activity was 16, thecomplex activity was 300, and the obtained polypropylene had a meltingpoint (Tm) of 152.4° C., a weight-average molecular weight (Mw) of0.5×10⁵ and a Q-value (Mw/Mn) of 2.5.

Example 36

(1) Synthesis of dimethylsilylenebis{1,1′-(2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride

5.5 ml of a cyclohexane/diethyl ether solution containing 5.9 mmol ofphenyl lithium (1.08 M) was dropped into 20 ml of a hexane solutioncontaining 1.54 g (5.9 mmol) of 2-benzyl-5-isopropylazulene, at 0° C.The resultant solution was stirred for 1.5 hours while the temperaturethereof was gradually raised to room temperature. Thereafter, thereaction solution was cooled to 0° C., and mixed with 20 ml oftetrahydrofuran and 11 μl (0.14 mmol) of dimethylaminopyridine andfurther with 0.36 g (3.0 mmol) of dichlorodimethylsilane. After thereaction solution was stirred for 3.5 hours while the temperaturethereof was gradually raised to 10° C., dilute hydrochloric acid wasadded thereto to terminate the reaction. The reaction solution wasseparated into organic and aqueous phases, and the organic phase wasextracted with hexane, dried with magnesium sulfate and stirred under areduced pressure to remove the solvent. The obtained product waspurified by a silica gel column chromatography (a mixed solvent:dichloromethane and n-hexane), thereby obtaining 1.7 g of dark greenpowder as a reaction product.

Next, 1.7 g of the thus-obtained reaction product was dissolved in 20 mlof diethyl ether. 2.9 ml of an n-hexane solution containing 4.7 mmol ofn-butyl lithium (1.59 M) was dropped into the diethyl ether solution at−5° C. After completion of the dropping, the reaction solution wasstirred for 3 hours while the temperature thereof was gradually raisedto 10° C. After the reaction solution was stirred under a reducedpressure to remove the solvent, 12 ml of a mixed solvent of toluene anddiethyl ether (20:1) was added thereto. After cooling to −78° C., thereaction solution was mixed with 0.55 g (2.4 mmol) of zirconiumtetrachloride. Thereafter, the reaction solution was stirred for 4 hourswhile the temperature thereof was gradually raised to room temperature,followed by further stirring at room temperature for 11 hours. Theobtained reaction solution was filtered through celite to separate asolid component therefrom. The thus-obtained solid component was washedwith 3 ml of toluene to recover a solid product. The thus-recoveredsolid product was extracted with dichloromethane and then the extractwas stirred under a reduced pressure to remove the solvent, therebyobtaining 0.23 g of a racemic and meso mixture of dimethylsilylenebis{1,1′-(2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconiumdichloride (yield: 11%).

The chemical shifts of ¹H-NMR of the above-obtained racemic and mesomixture are as follows.

300 MHz, CDCl₃ (ppm) 0.86 (s, meso SiMe), 0.90 (s, racemic SiMe), 0.96(s, meso SiMe), 1.07 (d, iPr-Me), 1.16 (d, iPr-Me), 2.5 (m, iPr-CH),3.7-4.0 (m, 2-CH₂), 4.85-5.00 (m, 4-H), 5.7-6.1 (m, —CH═), 6.4-7.5 (m,—CH═)

(2) Polymerization of Propylene Using Methylalumoxane as Co-catalyst

4 mmol (calculated as Al atom) of methylalumoxane (“MMAO” produced byTOSOH AKZO CORP.) was charged into a 2-liter stirring-type autoclave.Separately, 0.36 mg of the above-produced racemic and meso mixture wasdiluted with toluene, and then charged into a catalyst feeder equippedwith a safety rupture disc. Thereafter, 1,500 ml of propylene wasintroduced into the autoclave and the safety rupture disc of thecatalyst feeder was broken at room temperature. After the content of theautoclave was heated to 70° C., the polymerization of propylene wasconducted at that temperature for one hour, thereby obtaining 25 g ofpolypropylene. As a result of the measurements, it was confirmed thatthe complex activity was 7.0×10⁴, and the obtained polypropylene had amelting point (Tm) of 156.4° C., a melt flow rate (MFR) of 36, aweight-average molecular weight (Mw) of 1.6×10⁵ and a Q-value (Mw/Mn) of3.5.

Example 37

Polymerization of Propylene Using Clay Minerals as Co-catalyst

0.25 mmol (calculated as Al atom) of triisobutylaluminum (produced byTOSOH AKZO CORP.) was charged into a 1-liter stirring-type autoclave.Separately, 1.8 mg of the racemic and meso mixture obtained in Example36(1) was diluted with toluene, and then charged into a catalyst feederequipped with a safety rupture disc. Further, 50 mg of thetriethylaluminum-treated montmorillonite obtained in Example 35(1) and0.15 mmol (calculated as Al atom) of triisobutylaluminum were chargedinto the catalyst feeder. Thereafter, 700 ml of propylene was introducedinto the autoclave and the safety rupture disc of the catalyst feederwas broken at room temperature. After the content of the autoclave washeated to 80° C., the polymerization of propylene was conducted at thattemperature for one hour, thereby obtaining 0.5 g of polypropylene. As aresult of the measurements, it was confirmed that the catalyst activitywas 1, the complex activity was 37, and the obtained polypropylene had amelting point (Tm) of 147.6° C.

Example 38

(1) Synthesis of 9-silafluorene-9,9-diylbis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride

5.2 ml of a cyclohexane/diethyl ether solution containing 5.6 mmol ofphenyl lithium (1.08 M) was dropped into 10 ml of a hexane solutioncontaining 0.8 g (5.6 mmol) of 2-methylazulene, at −5° C. The resultantsolution was stirred for 2 hours while the temperature thereof wasgradually raised to room temperature. Thereafter, the reaction solutionwas cooled to 0° C., and mixed with 10 ml of tetrahydrofuran and 0.017 gof dimethylaminopyridine and further with 0.7 g (2.8 mmol) of9,9-dichloro-9-dimethylsilafluorene. After the reaction solution wasstirred at room temperature for one hour, dilute hydrochloric acid wasadded thereto to terminate the reaction. The reaction solution wasseparated into organic and aqueous phases, and the aqueous phase wasextracted with ether, the organic phases were combined, dried withmagnesium sulfate and stirred under a reduced pressure to remove thesolvent. The obtained product was purified by a silica gel columnchromatography (a mixed solvent: dichloromethane and n-hexane), therebyobtaining 0.9 g of dark green powder as a reaction product.

Next, 0.9 g of the thus-obtained reaction product was dissolved in 6 mlof diethyl ether. 1.98 ml of an n-hexane solution containing 2.9 mmol ofn-butyl lithium (1.47 M) was dropped into the diethyl ether solution at−78° C. After completion of the dropping, the reaction solution wasstirred for 4 hours while the temperature thereof was gradually raisedto room temperature. After the reaction solution was stirred under areduced pressure to remove the solvent, 15 ml of a mixed solvent oftoluene and diethyl ether (40:1) was added thereto. After cooling to−78° C., the reaction solution was mixed with 0.35 g (1.5 mmol) ofzirconium tetrachloride. Thereafter, the reaction solution was thetemperature thereof was immediately raised to room temperature, followedby further stirring at room temperature for 12 hours. The obtainedreaction solution stirred under a reduced pressure to remove thesolvent, and then mixed with toluene to form a suspension. Thesuspension was filtered through celite in the presence of a nitrogenstream to separate a solid component therefrom. The thus-obtained solidcomponent was washed with toluene, and then extracted withdichloromethane. Thereafter, the extract was stirred under a reducedpressure to remove dichloromethane contained as a solvent therein,thereby obtaining 0.25 g of a racemic and meso mixture of9-silafluorene-9,9-diyl bis{1,1′-(2-methyl-4-phenyl-4-hydroazulenyl)}zirconium dichloride (yield: 22%).

The chemical shifts of ¹H-NMR of the above-obtained racemic and mesomixture are as follows.

300 MHz, CDCl₃ (ppm) 2.40 (s, meso 2-Me), 2.44 (s, racemic 2-Me), 5.01(br s, racemic 4-H), 5.03 (br s, meso 4-H), 5.8-6.2 (m, —CH═), 7.1-7.7(m, —CH═), 7.9-8.1 (m, —CH═), 8.3-8.5 (m, —CH═)

(2) Polymerization of Propylene Using Methylalumoxane as Co-catalyst

2 mmol (calculated as Al atom) of methylalumoxane (“MMAO” produced byTOSOH AKZO CORP.) was charged into a 1-liter stirring-type autoclave.Separately, 0.1 mg of the above-produced racemic and meso mixture wasdiluted with toluene, and then charged into a catalyst feeder equippedwith a safety rupture disc. Thereafter, 700 ml of propylene wasintroduced into the autoclave and the safety rupture disc of thecatalyst feeder was broken at room temperature. After the content of theautoclave was heated to 70° C., the polymerization of propylene wasconducted at that temperature for one hour, thereby obtaining 20 g ofpolypropylene. As a result of the measurements, it was confirmed thatthe complex activity was 20×10⁴, and the obtained polypropylene had amelting point (Tm) of 152.8° C. and a melt flow rate (MFR) of 1.3.

Example 39

Polymerization of Propylene Using Methylalumoxane as Co-catalyst

500 ml of toluene was charged into a 1-liter stirring-type autoclave.Successively, 2.1 mmol (calculated as Al atom) of methylalumoxane(“MMAO” produced by TOSOH AKZO CORP.) and 0.3 mg of the racemic and mesomixture obtained Example 38(1) were diluted with toluene, and thencharged into the autoclave. Thereafter, propylene was introduced intothe autoclave. After the content of the autoclave was heated to 70° C.,the polymerization of propylene was conducted at that temperature forone hour while the propylene pressure in the autoclave was maintained at5 kgf/cm²G, thereby obtaining 4 g of polypropylene. As a result of themeasurements, it was confirmed that the complex activity was 1.3×10⁴,and the obtained polypropylene had a melting point (Tm) of 156.2° C.

Example 40

Polymerization of Propylene Using Clay Minerals as Co-catalyst

(1) Chemical Treatment of Clay Minerals and Preparation of SolidCatalyst Component

The same procedure as defined in Example 11(2) was conducted to obtain amontmorillonite/toluene slurry having a montmorillonite content of 33mg/ml.

(2) Polymerization of Propylene

0.25 mmol (calculated as Al atom) of triisobutylaluminum (produced byTOSOH AKZO CORP.) was charged into a 1-liter stirring-type autoclave.Separately, 3 mg of the racemic and meso mixture obtained in Example38(1) was diluted with toluene, and then charged into a catalyst feederequipped with a safety rupture disc. Further, the above-prepared tolueneslurry containing 50 mg of montmorillonite and 0.15 mmol (calculated asAl atom) of triisobutylaluminum were charged into the catalyst feeder.Thereafter, 700 ml of propylene was introduced into the autoclave andthe safety rupture disc of the catalyst feeder was broken at roomtemperature. After the content of the autoclave was heated to 80° C.,the polymerization of propylene was conducted at that temperature forone hour, thereby obtaining 72 g of polypropylene. As a result of themeasurements, it was confirmed that the catalyst activity was 1.4×10³,the complex activity was 3.0×10⁴, and the obtained polypropylene had amelting point (Tm) of 147.9° C. and a melt flow rate (MFR) of 21.3.

What is claimed is:
 1. A process for producing a polymer of α-olefin ,comprising contacting a catalyst with α-olefin to conduct polymerizationor copolymerization of α-olefin, which catalyst comprises: an essentialcomponent (A) of a transition metal compound; an essential component (B)of an ion exchangeable layer compound except for silicate or aninorganic silicate; and an optional component (C) of an organoaluminumcompound; said component (A) being represented by the following generalformula (III)

 wherein R¹, R², R⁴ and R⁵ are independently a hydrogen atom, ahydrocarbon group having 1 to 10 carbon atoms, a silicon-containinghydrocarbon group having 1 to 18 carbon atoms or a halogenatedhydrocarbon group having 1 to 18 carbon atoms; R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵ and R¹⁶ are each independently a hydrogen atom, a hydrocarbongroup having 1 to 20 carbon atoms or a halogenated hydrocarbon grouphaving 1 to 20 carbon atoms; Q is a bridging group of the two 5-memberedrings, and is a divalent hydrocarbon group having 1 to 20 carbon atoms,a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, asilylene group, a silylene group having a hydrocarbon group or ahalogenated hydrocarbon group having 1 to 20 carbon atoms, anoligosilylene group, an oligosilylene group having a hydrocarbon groupor halogenated hydrocarbon group having 1 to 20 carbon atoms, agermylene group or a germylene group having a hydrocarbon group orhalogenated hydrocarbon group having 1 to 20 carbon atoms; X and Y areindependently a hydrogen atom, a halogen atom, a hydrocarbon grouphaving 1 to 20 carbon atoms, a silicon-containing hydrocarbon grouphaving 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20carbon atoms, an amino group or a nitrogen-containing hydrocarbon grouphaving 1 to 20 carbon atoms; Ph is a phenyl group; and M is a transitionmetal selected from the group consisting of elements belonging to Group4-6 of the Periodic Table.
 2. A process for producing a polymer ofα-olefin according to claim 1, wherein in formula (III), R¹ and R⁵ are ahydrogen atom, R² and R⁴ are a methyl group, R⁹, R¹⁰, R¹¹, R¹², R¹³,R¹⁴, R¹⁵ and R¹⁶ are a hydrogen atom, M is zirconium, Q is adimethylsilylene group, and X and Y are a halogen atom.
 3. A process forproducing a polymer of α-olefin according to claim 1, wherein in formula(III), R¹ and R⁵ are a hydrogen atom, R² and R⁴ are a methyl group, R⁹,R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are a hydrogen atom, M is hafnium,Q is a dimethylsilylene group, and X and Y are a halogen atom.
 4. Aprocess for producing a polymer of α-olefin according to claim 1,wherein in formula (III), R¹ and R⁵ are a hydrogen atom, R² and R⁴ are aethyl group, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ are a hydrogenatom, M is zirconium, Q is a dimethylsilylene group, and X and Y are ahalogen atom.
 5. A process for producing a polymer of α-olefin accordingto claim 1, wherein in formula (III), R¹ and R⁵ are a hydrogen atom, R²and R⁴ are a methyl group, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, R¹⁵ and R¹⁶ area hydrogen atom, M is zirconium, Q is a dimethylgermylene group, and Xand Y are a halogen atom.
 6. A process for producing a polymer ofα-olefin according to claim 1, wherein in formula (III), R¹ and R⁵ are ahydrogen atom, R² and R⁴ are a ethyl group, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴,R¹⁵ and R¹⁶ are a hydrogen atom, M is zirconium, Q is adimethylgermylene group, and X and Y are a halogen atom.